US7591921B2 - Heat-decaying materials, transfer sheet using the same, and patterning method - Google Patents

Heat-decaying materials, transfer sheet using the same, and patterning method Download PDF

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US7591921B2
US7591921B2 US10/532,747 US53274705A US7591921B2 US 7591921 B2 US7591921 B2 US 7591921B2 US 53274705 A US53274705 A US 53274705A US 7591921 B2 US7591921 B2 US 7591921B2
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heat
decaying
resin
sheet
group
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US20050276934A1 (en
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Hiroji Fukui
Toshio Enami
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Sekisui Chemical Co Ltd
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    • H05K3/048—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer using a lift-off resist pattern or a release layer pattern
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11—Methods of delaminating, per se; i.e., separating at bonding face
    • Y10T156/1153—Temperature change for delamination [e.g., heating during delaminating, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer

Definitions

  • the present invention relates to a heat-decaying material, a transfer sheet using the same, and a patterning method.
  • the invention relates to a heat-decaying material that hardly deteriorates and decomposes at ordinary service temperatures but can decay within a short period of time when heated at relatively low temperature, and to its use.
  • adhesive tapes are stuck to surfaces for temporary fixation in predetermined positions of parts to be bonded together or parts to be bonded to housings or parts to be bonded to substrates in assembly processes, or for protection of surfaces that are readily scratched during working or conveyance.
  • adhesive tapes are used for such temporary fixation or surface protection, there are some problems in that peeling them is often difficult and, when they are peeled, the objects may be scratched or paste may remain on the objects.
  • resin adhesives may readily melt or decompose when heated at 400° C. or higher, and the structures bonded with them may be thereby readily dismantled.
  • the structures themselves would be deteriorated and denatured, and it causes a problem in that the dismantled structures could not be recycled.
  • a transfer sheet with an adhesive sheet is utilized as an efficient transfer method, since multiple parts disposed on the sheet may be transferred all at a time.
  • the adhesive sheet acts also as a reinforcing material for the parts to be transferred, and, for example, it enables transfer of even brittle parts such as ultra-thin semiconductor wafers and semiconductor chips with no damage thereto.
  • the transfer sheet must have a high adhesive force to objects before they are transferred, and must readily release them when they are transferred.
  • adhesive sheets that have a high adhesive force for the necessary period of time but, on the other hand, may be readily peeled from objects when the objects are to be released from them are needed in many applications.
  • the adhesive sheets of the type those capable of reducing their adhesive force when some stimulation is applied to the adhesive matter thereof are known, and they include, for example, heat-foaming adhesive sheets, thermosetting adhesive sheets, photocurable adhesive sheets.
  • heat-foaming adhesive sheets thermosetting adhesive sheets
  • photocurable adhesive sheets thermocurable adhesive sheets.
  • their adhesive force that may be reduced is limited, and, in fact, some adhesive sheets could not have a sufficiently high adhesive force before transfer, or some others could not sufficiently reduce their adhesive force in transfer.
  • Patent Reference 1 discloses a heat-decaying adhesive sheet that may decay by at least 95% of the sheet weight when heated at 700° C. or lower for 30 minutes or shorter. When the heat-decaying adhesive sheet is used, then the sheet itself may be removed when heated.
  • Patent Reference 1 says that the heat-decaying adhesive sheet is resistant to explosion-proofing treatment of Brawn tubes, and does not decay even when heated at 450 to 550° C. for a short period of time. From this, it is considered that the sheet may take ten and a few minutes before it decays at a temperature of 450° C. or lower. It is considered that the long-term heating at such high temperatures may cause deterioration and denaturation of objects.
  • Patent Reference 2 discloses a binder for ceramic shaping, which comprises a water-soluble polyalkylene glycol, a novel combed hydrophobic diol and a polyisocyanate, and which is such that its heat generation in degreasing is slow, the amount of its heat generation is small and the degree of carbon residue from it is small.
  • the binder resin disclosed in Patent Reference 2 is an urethane resin obtained through reaction of diol and isocyanate, and, therefore, its decomposition residue may be small but it is problematic in that it leaves an yellowed residue that may be an oxide derived from the urethane bond. Accordingly, clean surfaces are often difficult to obtain in some cases.
  • interlayer insulating films are used for forming interlayer insulating films in semiconductor devices and multi-level wiring boards.
  • the interlayer insulating films of the type are formed of an insulating material having a low dielectric constant.
  • Patent Reference 3 discloses a method for producing a porous film by thermally processing a film of a uniformly-dissolved composite material that comprises a partially-hydrolyzed condensate of an alkoxysilane and a fluororesin having a carboxylic acid group in the molecule and having a fluorine-containing aliphatic cyclic structure or a fluorine-containing aliphatic structure in the backbone chain thereof, at a temperature not lower than the thermal decomposition-initiating temperature of the fluororesin.
  • interlayer insulating films in semiconductor devices, they are formed after the formation of elements on semiconductor substrates, and therefore, when the semiconductor substrates with elements thereon are exposed to high temperatures for a long period of time, then the elements may be deteriorated. Accordingly, it is desired to develop interlayer insulating films capable of being formed at low temperatures.
  • Recent ICs and LSIs are to have much more increased degree of integration and are to be much more micropatterned, and more than these, high-density packaging techniques are greatly developing.
  • electronic system integration techniques are much desired, which are for integrating and systemizing various functional blocks such as optical devices and high-frequency devices that comprise multiple LSIs and compound semiconductors, for example, for system-in-packages.
  • conductive fine particles For bonding such conductive fine particles to electrodes, heretofore employed is a method of making multiple conductive fine particles sucked by a suction pad having multiple vacuum suction nozzles, and putting the conductive fine particles on multiple electrodes all at a time, and bonding them to the electrodes.
  • the electrode face of the electronic parts is previously coated with an organic acid ester.
  • the organic acid ester is effective for removing the spontaneous oxide film formed on the electrode surface and for facilitating the capture of the conductive fine particles.
  • the conductive fine particles thus put on the electrode are still problematic in that they may shift from the electrode while conveyed to the next step.
  • the conductive fine particles In the method of disposing conductive fine particles by the use of vacuum suction nozzles, the conductive fine particles must be sucked by all the vacuum suction nozzles, but suction failures may occur and the method is not always a sure method. In addition, since the conductive fine particles are only sucked, they may drop off if the operation speed is increased. Further, since the electrode position for electronic parts differs for every electronic part, and the method has still another problem in that vacuum suction nozzles corresponding to all electronic parts must be developed.
  • the method comprises disposing conductive fine particles on electrodes by the use of a conductive particles transfer sheet that has conductive fine particles previously disposed on an adhesive sheet.
  • the method comprises applying a conductive particles transfer sheet to electronic parts in such a manner that the position of the conductive fine particles corresponds to the position of the electrode, then melt-bonding the conductive fine particles to the electrode, and thereafter peeling the adhesive sheet.
  • the adhesive used in the adhesive sheet is a specific one capable of reducing its adhesive force by imparting specific energy thereto, then the adhesive sheet may be readily peeled off not breaking the connection of the conductive fine particles once melt-bonded to the electrodes.
  • the adhesive sheet of the type for example, a heat-foaming adhesive sheet, a thermosetting adhesive sheet and a photocurable adhesive sheet have been proposed.
  • the most important elementary technique is a fine bonding technique.
  • one typical bonding technique for it is a bump-bonding technique.
  • further increase in the accuracy in the bump bonding technique is to be an important theme in the art.
  • the related art has various problems as mentioned above, and a technique of fully ensuring high producibility and high bonding reliability in bump formation on electrodes of electronic parts is now greatly desired.
  • circuit boards to be built in these electronic appliances are desired to be much more down-sized and thin-sized.
  • circuit boards suitable to high-speed operation that enables accurate switching to high-frequency signals.
  • circuit boards it is desired to shorten the wiring length and to reduce the wiring width and the wiring distance for the purpose of shortening the time necessary for electric signal propagation.
  • circuit boards are desired to have an increased wiring density so as to attain high-density packaging thereon, in accordance with the recent tendency toward down-sized and high-speed-operable electronic appliances.
  • circuit transfer tape an adhesive tape prepared by forming a metal foil circuit pattern on the surface thereof (circuit transfer tape) to an insulating substrate to thereby embed the circuit pattern into the insulating substrate, and thereafter peeing the adhesive tape from the circuit pattern so as to transfer the circuit pattern onto the insulating substrate.
  • a circuit transfer tape 2101 is prepared.
  • the circuit transfer tape 2101 comprises an adhesive tape 2102 and a metal layer 2103 to form a circuit pattern on its surface. After this is positioned to an insulating substrate 2104 , the two are bonded to each other.
  • the insulating substrate 2104 is a semi-cured prepreg. In this case, the two are bonded in a mode of thermal pressure bonding, for example, under a pressure of 100 kg/cm 2 or so, and as in FIG. 10( b ), a part or all of the metal layer 2103 is embedded and fixed in the insulating substrate 2104 .
  • the adhesive tape 2102 is peeled from the insulating substrate 2104 , whereby a metal layer 2103 having a circuit pattern is transferred onto the insulating substrate 2104 to form a single-layered circuit board. Further, if desired, the insulating substrate 2104 is completely cured.
  • a multi-layered circuit board may be formed by laminating the above-mentioned single-layered circuit boards.
  • the adhesive component of the adhesive tape 2102 is contacted with the insulating substrate 2104 and the adhesive tape 2102 is often difficult to peel from the insulating substrate 2104 .
  • the semi-cured insulating substrate 2104 may be deformed while the adhesive tape 2102 is peeled off, whereby the wiring distance of the metal layer 2103 may be disordered and the wiring planarity may be lost, or that is, the circuit pattern may be disordered, and, in addition, the embedded metal layer 2103 may be peeled off along with the adhesive tape 2102 .
  • Patent Reference 5 discloses a method for producing a circuit board, which comprises using a circuit transfer tape with a layer of a photocrosslinkable adhesive component having high adhesiveness formed thereon, and in which the circuit transfer tape is exposed to light from the side of the circuit pattern thereof so as to lower the adhesive force of the tape on the side with no circuit pattern formed thereon, and therefore even when the adhesive component of the circuit transfer tape is contacted with an insulating substrate, it does not adhere to the insulating substrate and the circuit pattern can be thereby well transferred onto the insulating substrate with no pattern disturbance.
  • a resist pattern is formed through photolithography, and various materials of conductor films, semiconductor films or insulator films for semiconductor devices are patterned through etching via the resist pattern serving as a mask (for example, see Non-Patent Reference 1).
  • the resist pattern is used as a mask for plating, and a metal film of copper (Cu) or gold (Au) may be patterned.
  • the patterning process through such photolithography is at present the most popular process in patterning not only for production of semiconductor devices but also for production of any other various display devices or micromachines.
  • FIG. 16 and FIG. 17 are cross-sectional views showing a process scheme of forming a resist pattern through photolithography and forming a pattern on an insulator film by the use of the resist pattern serving as an etching mask.
  • an insulator film 3102 of silicon oxide is formed on a semiconductor substrate 3101 with various semiconductor elements (not shown) formed thereon, and a resist film 3103 is formed on the insulator film 3102 in a coating process of photolithography.
  • the resist film 3103 is formed of a photosensitive resin, and its formation is as follows: Concretely, a polymer of a photosensitive resin composition or the like is dissolved in a solvent to prepare a resist coating solution, and this is applied onto a semiconductor wafer, the insulator film 3102 formed on the semiconductor substrate 3101 in a mode of spin coating. After thus spin-coated, this is prebaked at a temperature not higher than 100° C. so as to vaporize away the unnecessary solvent. In that manner, the resist film 3103 is formed.
  • the resist film 3103 is exposed to light 3107 in an ordinary reduction projection exposure manner for pattern exposure transfer to it. In that manner, an optical pattern transfer region 3103 a is formed in a predetermined region of the resist film 3103 .
  • this is heat-treatment for PEB (post exposure baking).
  • the recent exposure light 3107 is an ArF excimer laser (wavelength: about 193 nm), and the resist film 3103 is a chemical amplification-type resist.
  • the semiconductor substrate 3101 that is in a semiconductor wafer condition is dipped in a developer. If desired, this may be exposed to shower of a developer. In that manner, the optical pattern transfer region 3103 a is removed through the development to form a resist pattern, as in FIG. 16( c ). Further, this is post-baked at a temperature of 120° C. or so, thereby forming a resist mask 3108 on the insulator film 3102 . This is a case where the resist is a positive resist. The other case where the resist is a negative resist is contrary to it, in which the optical pattern transfer region 3103 a remains through the development and the other region is removed.
  • the insulator film 3102 is dry-etched by the use of plasma, as in FIG. 17 . With that, an opening 3109 is formed in the insulator film 3102 .
  • the resist mask is stripped off.
  • the resist mask 3108 is ashed away in oxygen (O 2 ) plasma.
  • O 2 oxygen
  • a pattern of the insulator film 3102 having the opening 3109 is formed.
  • the opening 3109 is generally to be a via-hole for wiring interconnection via the insulator film 3102 that serves as a wiring interlayer insulation film.
  • the pattern dimension in patterning semiconductor devices has become significantly micro-sized to a level of 100 nm or less.
  • semiconductor devices are therefore much more improved to have an increased degree of integration and to be multi-functional high-performance devices.
  • the above-mentioned micropatterning technique in the above-mentioned photolithography technology requires the above-mentioned high-level techniques of coating, exposure, development and stripping, and it increases the production costs in the process of patterning semiconductor devices.
  • Patent Reference 1 JP-A 11-293207 [Patent Reference 2] JP-A 2000-355618 [Patent Reference 3] JP-A 11-217458 [Patent Reference 4] JP-A 11-168123 [Patent Reference 5] JP-A 10-178255 [Non-Patent Reference 1] Semiconductor Handbook, 2nd Ed., edited by Semiconductor Handbook Edition Association, published by Ohm, May, 25, 1994, pp. 198-199.
  • an object of the present invention is to provide a heat-decaying material which hardly deteriorates or decomposes at ordinary service temperatures but which may decay within a short period of time when heated at relatively low temperatures.
  • Another object of the invention is to solve the above-mentioned drawbacks in the related art and to provide a method for producing a porous film in which sufficiently large pores may be formed uniformly and the material to form the holes do not remain, and also to provide a porous film obtained according to the production method.
  • the invention has been made in consideration of the current situation as above, and its object is to provide a transfer sheet that has the following advantages: Using it, conductive fine particles may be disposed on the electrodes of electronic parts not being shifted or dropped from it; or multiple conductive fine particles may be surely and readily melt-bonded to the electrodes of electronic parts, all at a time thereon. Even when the line width of circuit patterns is thinned, the circuit pattern may be transferred onto a semi-cured insulating substrate or a ceramic green sheet, not being disordered. Accordingly, using the transfer sheet makes it possible to obtain high-density and high-accuracy micropatterned wiring circuit boards.
  • Still another object of the invention is to provide a novel technique for patterning so as to provide a patterning method that makes it possible to simplify the above-mentioned series of techniques and to reduce the costs of the patterning technique.
  • the invention is as follows:
  • a heat-decaying material comprising a polyoxyalkylene resin as the principal ingredient thereof, which has an oxygen atom content of from 15 to 55% by mass and of which at least 95% by weight decays within 10 minutes when heated at a predetermined temperature falling between 150 and 350° C.
  • polyoxyalkylene resin is polyoxypropylene, polyoxyethylene, polyoxytetramethylene, or a mixed resin of polyoxypropylene, polyoxyethylene and/or polyoxytetramethylene.
  • a heat-decaying material of a heat-decaying sheet which is composed of the heat-decaying material of any of above (1) to (13) and which keeps its sheet form at a temperature of 100° C. or lower.
  • a heat-decaying material comprising the heat-decaying material of any of above (1) to (13), which contains a crosslinkable functional group-having polymer that contains segments of a crosslinkable functional group-having polyoxyalkylene glycol or polyoxyalkylene, and a crosslinking agent, and which has a viscosity at 20° C. of from 1 to 5,000,000 mPa•s.
  • crosslinkable functional group is at least one selected from a hydrolyzing silyl group, an isocyanate group, an epoxy group, an oxetanyl group, an acid anhydride group, a carboxyl group, a hydroxyl group, and a polymerizable unsaturated hydrocarbon group.
  • a method for producing a porous material which comprises:
  • the method for producing a porous material as above wherein the precursor is a composite prepared through partial hydrolysis condensation of the skeleton-forming crosslinkable material (a), and the composite is applied onto the substrate to be processed and then this is heated.
  • the method for producing a porous material as above wherein the heating of the precursor is effected in two stages, a first heating, and a second heating at a temperature higher than the temperature in the first heating.
  • a transfer sheet constructed by adhering a transfer object on a heat-decaying adhesive resin layer that comprises the heat-decaying material of above (1).
  • the transfer sheet as a conductive particles transfer sheet, which has conductive fine particles adhered to and disposed on a heat-decaying adhesive resin sheet.
  • the conductive particles transfer sheet wherein the conductive fine particles are embedded in the heat-decaying adhesive resin sheet from its top face toward its back face.
  • the conductive particles transfer sheet wherein the conductive fine particles are for bump-bonding between electrodes of an electronic part, and are melt-bonded on the electrodes.
  • the conductive particles transfer sheet wherein the electronic part is a semiconductor chip, a resin-encapsulated semiconductor device or a wiring board.
  • the conductive particles transfer sheet wherein the conductive fine particles have solder at least on their surface.
  • the conductive particles transfer sheet wherein the conductive fine particles are to form solder ball bumps in BGA packages.
  • the conductive particles transfer sheet wherein the conductive fine particles are to from bumps on semiconductor chips.
  • a method for bonding conductive fine particles to the electrode face of electronic parts which comprises attaching a conductive particles transfer sheet to electronic parts where conductive fine particles are disposed on the heat-decaying adhesive sheet comprising the heat-decaying material of above (1) in such a manner that the conductive fine particles could be in contact or in no contact with the position of the electrodes of the electronic parts, then melting and bonding the conductive fine particles to the electrodes of the electronic parts, and heating the resulting structure to decay the heat-decaying adhesive sheet.
  • a method for bonding conductive fine particles to electrodes which comprises casting a paste of the heat-decaying material of above (1) on the surface of electronic parts with electrode face formed thereon, to thereby form a heat-decaying resin layer on them, disposing and bonding conductive fine particles to the electrode face via the heat-decaying resin layer, then melting and bonding the conductive fine particles to the electrodes of the electronic parts, and heating the resulting structure to decay the heat-decaying adhesive sheet.
  • a method for bonding conductive fine particles to electrodes which comprises applying a solution that contains a composition of the heat-decaying material of above (1) to the surface of electronic parts with electrode face formed thereon, forming a heat-decaying resin layer from the coating film, disposing and bonding conductive fine particles to the electrode face via the heat-decaying resin layer, then melting and bonding the conductive fine particles to the electrodes of the electronic parts, and heating the resulting structure to decay the heat-decaying adhesive sheet.
  • the transfer sheet as above, wherein the part to be transferred is an electrode pattern.
  • the transfer sheet as above which is a transfer sheet for circuit formation and which comprises:
  • the transfer sheet as above which is a transfer sheet for circuit formation and which comprises:
  • a metal foil or conductive paste layer formed on the surface of the adhesive sheet.
  • a transfer sheet for circuit formation which comprises:
  • a transfer sheet for circuit formation which comprises:
  • a transfer sheet for circuit formation which comprises:
  • thermoforming material of above (1) further contains a crosslinkable resin component that crosslinks through energy stimulation thereto.
  • a method for producing a circuit board by using the transfer sheet for circuit formation as above which comprises:
  • a method for producing a circuit board by using the transfer sheet for circuit formation as above which comprises:
  • thermoforming a circuit board as above, wherein the heat-decaying material comprises a crosslinkable silyl group-having polyoxyalkylene resin, and the heating temperature is controlled to fall between 150° C. and 170° C.
  • a patterning method which comprises a step of forming a heat-decaying resin film of the heat-decaying material of above (1) on the surface of a substrate to be processed, and a step of selectively applying thermal energy to the heat-decaying resin film so as to decay the heat-decaying resin film in the thermal energy-irradiated area to thereby form a pattern of the heat-decaying resin film.
  • a patterning method which comprises:
  • thermoforming resin film comprises a crosslinkable silyl group-having polyoxyalkylene resin composition.
  • the patterning method as above wherein the substrate to be processed is selectively etched via the pattern of the heat-decaying resin material serving as an etching mask, and then this is heated so as to decompose and remove the pattern of the heat-decaying resin.
  • the patterning method as above which includes:
  • the patterning method as above which includes:
  • the heat-decaying material of the invention hardly deteriorates and decomposes at room temperature, but may decay within a short period of time when heated at relatively low temperatures.
  • the polyoxyalkylene resin in the heat-decaying material of the invention may be polyoxypropylene, polyoxyethylene, polyoxytetramethylene, or a mixed resin of polyoxypropylene, polyoxyethylene and/or polyoxytetramethylene. Accordingly, for this, polyoxypropylene having a low cohesion force may be combined with polyoxyethylene and/or polyoxytetramethylene having a high cohesion force, and the cohesion force of the decaying material of the invention can be controlled in any desired manner according to the use and the application thereof.
  • the polyoxypropylene content of the mixed resin may be at least 50% by mass, and the decaying temperature and the decaying time of the material can be suitably controlled.
  • the polyoxyalkylene resin may have a number-average molecular weight of from 500 to 5,000,000. Therefore, the resin is not so much volatile, and the decaying material of the invention can be stably handled, and rapid decaying of the material could be more ensured.
  • the heat-decaying material of the invention may contain a decomposition promoter, and it can be decayed at lower temperatures within a shorter period of time.
  • the decomposition promoter that may be in the heat-decaying material of the invention may be a peroxide, and the decomposition residue from the decomposition promoter may be reduced.
  • the decomposition promoter that may be in the heat-decaying material of the invention may be an azo compound.
  • the promoter may promote the decomposition and, in addition, the nitrogen gas to be generated through decomposition of the azo compound may promote the volatility of the decomposed products.
  • the heat-decaying material of the invention may contain a decomposition retardant, and the decaying time and the time may be controlled in accordance with various applications of the material.
  • the decomposition retardant may be any of a mercapto compound, an amine compound, an organic tin, or an organic boron. Accordingly, decomposition of the polyoxyalkylene that constitutes the heat-decaying material of the invention may be retarded.
  • the heat-decaying material of the invention may be decomposed more rapidly in an oxygen-containing atmosphere, and may be decomposed at lower temperatures, and, in addition, the decomposition residue may be reduced. Taking advantage of this property, the heat-decaying material may be decayed when heated at a temperature falling between 150 and 300° C. in an oxygen-containing atmosphere, if it could not be heated to its intrinsic decomposition temperature. Accordingly, the material may be applied in various fields.
  • the decomposition speed of the heat-decaying material of the invention lowers in an anaerobic atmosphere. Accordingly, when the material is used in formation of micropatterns, then high-accuracy micropatterns may be formed. In an anaerobic atmosphere, the decomposition temperature of the material may be high. When the material is heated and decayed at a predetermined temperature falling between 150 and 350° C. in an anaerobic atmosphere, then it does not decay at its intrinsic decomposition temperature, and its application ranges may be further broadened.
  • the heating temperature for the material may be lowered.
  • the material does not decompose at a temperature at which it decomposes in air, and the material may be so controlled that it begins to decompose at a higher temperature. Accordingly, depending on the oxygen concentration in an atmosphere, the decomposition temperature of the heat-decaying material may be controlled in a broad range.
  • the volatility of the decomposition residue from the heat-decaying material of the invention increases, and therefore the residue may be reduced.
  • the heating time for the material may be shortened. Accordingly, the invention is applicable to materials that may be readily damaged under heat.
  • the heat-decaying material of the invention may form a heat-decaying sheet having a sheet form at a temperature not higher than 100° C.
  • the polyoxyalkylene resin may be an uncrosslinked one having a number-average molecular weight of from 5000 to 5,000,000. Even when the resin therein is an uncrosslinked polyalkylene resin, the material may favorably keep its sheet form at room temperature.
  • the heat-decaying material of the invention may contain a crosslinked polyoxyalkylene resin. Even though not reinforced by a substrate, the material may favorably keep its sheet form at room temperature.
  • the crosslinked polyoxyalkylene resin may be formed by crosslinking a crosslinkable functional group-having polymer that contains segments of a crosslinkable functional group-having polyalkylene glycol or polyoxyalkylene, with a crosslinking agent.
  • a crosslinkable functional group-having polymer that contains segments of a crosslinkable functional group-having polyalkylene glycol or polyoxyalkylene
  • the heat-decaying material of the invention contains an uncrosslinked polymer that contains segments of an uncrosslinked polyalkylene glycol or polyoxyalkylene glycol, it may be reinforced with a substrate and it may favorably keep its sheet form at room temperature.
  • the heat-decaying material of the invention When the heat-decaying material of the invention is reinforced with a substrate, it may favorably keep its sheet form even at room temperature even when it contains an uncrosslinked polyoxyalkylene resin.
  • the heat-decaying material of the invention may contain a crosslinkable functional group-having polymer that contains segments of a crosslinkable functional group-having polyoxyalkylene glycol or polyoxyalkylene, and a crosslinking agent, and may have a viscosity at 20° C. of from 1 to 5,000,000 mPa•s.
  • the material hardly deteriorates or decomposes and may keep its paste form, and when exposed to light or the like, it is crosslinked into a cured product.
  • the cured product When the cured product is heated at relatively low temperatures, it may readily decay within a short period of time.
  • the heat-decaying material of the invention may contain at most 30% by mass of a polymerizable unsaturated group-having compound. Maintaining the above-mentioned properties thereof, the heat-decaying material of the type may ensure more rapid curability.
  • the heat-decaying material of the invention may have a viscosity at 20° C. of from 1 to 100 mPa•s. Accordingly, it can be uniformly formed in any desired region according to a spin-coating process, a pulling-up process or a dipping process.
  • the heat-decaying material of the invention may have a viscosity at 20° C. of from 500 to 100,000 mPa•s. Accordingly it can be formed in any desired region according to a brush-coating process.
  • the heat-decaying material of the invention may have a viscosity at 20° C. of from 200 to 1000 mPa•s. Accordingly, it can be formed to have any desired pattern according to a screen-printing process.
  • the crosslinkable functional group may be at least one selected from a hydrolyzing silyl group, an isocyanate group, an epoxy group, an oxetanyl group, an acid anhydride group, a carboxyl group, a hydroxyl group, and a polymerizable unsaturated hydrocarbon group. Accordingly, any known crosslinking condition may be selected for the material, and the crosslinking reaction of the material may be readily controlled.
  • a known crosslinking agent for example, Lewis acids such as organic tin, organic aluminium, organic boron; inorganic acids such as hydrochloric acid; or triethylamine, ammonia or sodium hydroxide may be used.
  • a known crosslinking agent such as polyalcohols, polyamines, organic tin, or compounds having plural acid anhydride structures in one molecule may be used.
  • a known crosslinking agent such as compounds having plural primary amino groups, tertiary amines, compounds having plural carboxyl groups, optical acid generators, optical amine generators, or compounds having plural acid anhydride structures in one molecule may be used.
  • the group is an oxetanyl group
  • a known crosslinking agent such as optical acid generators may be used.
  • the group is an acid anhydride group
  • a known crosslinking agent such as polyalcohols, or compounds having plural primary amino groups may be used.
  • a known crosslinking agent such as compounds having plural epoxy groups, or compounds having plural hydroxyl groups may be used.
  • a known crosslinking agent such as compounds having plural isocyanate groups may be used.
  • the group is a polymerizable unsaturated hydrocarbon group
  • a known crosslinking agent such as organic peroxides, polymercaptans, or compounds having plural primary amino groups may be used.
  • the heat-decaying material of the invention may decay in a temperature atmosphere falling between 150 and 220° C. Accordingly, this can be decayed in temporary fixation in optical structures, or in packaging for producing semiconductor devices with low-temperature solder, and, therefore, the material can be used for temporary fixation or for other various purposes.
  • the heat-decaying material of any of the invention may decay in a temperature atmosphere falling between 220 and 280° C. Accordingly, it can be decayed in packaging for producing semiconductor devices with lead-free solder, and therefore, the material can be used for temporary fixation or for other various purposes.
  • the heat-decaying material of the invention may decay in a temperature atmosphere falling between 280 and 350° C. Accordingly, the material is applicable to a case where a porous thin film is formed on aluminium wiring, and it can be used in various applications.
  • the cured product of the heat-decaying material of any of the invention may decay in a temperature atmosphere falling between 150 and 220° C. Accordingly, the material can be decayed in temporary fixation in optical structures, or in packaging for producing semiconductor devices with low-temperature solder, and, therefore, the material can be used for temporary fixation or for other various purposes.
  • the cured product of the heat-decaying material of the invention may decay in a temperature atmosphere falling between 220 and 280° C. Accordingly, the material can be decayed in packaging for producing semiconductor devices with lead-free solder, and therefore, the material can be used for temporary fixation or for other various purposes.
  • the cured product of the heat-decaying material of the invention may decay in a temperature atmosphere falling between 280 and 350° C. Accordingly, the material is applicable to a case where a porous thin film is formed on aluminium wiring, and it can be used in various applications.
  • a skeleton-forming crosslinkable material and the heat-decaying material are heated in a uniformly dispersed condition of the two, and the heat-decaying material can be well decayed under heat at low temperatures. Accordingly, the resulting pores can be uniformly dispersed in the porous material produced in such a manner that the skeleton-forming crosslinkable material surrounds the pores and forms a stiff skeleton phase structure. Therefore, in a process of producing semiconductor devices, the film can be formed not having any negative influence on the other element region.
  • the skeleton phase-constituting crosslinkable material can be selected in any desired manner, and porous materials of high reliability can be formed in accordance with the use thereof. Further, since porous materials of good film quality can be formed at low temperatures falling between 150 and 350° C., preferably between 150° C. and 200° C., the latitude in selecting the skeleton phase-constituting crosslinkable material is broad. In particular, when the porous material is used as interlayer insulating films in semiconductor devices, then it can be formed at extremely low temperatures not higher than 200° C., and this means that the films can be formed with no deterioration of elements.
  • any of spin-coating method or screen-printing method may be suitably selected by controlling the composition for the films.
  • porous sheets are easy to form.
  • the porous sheet may be stuck to the surface of a semiconductor substrate by the sue of an adhesive resin, and it may be used as an interlayer insulating film.
  • the heating may be effected at a temperature falling between 150 and 350° C. and for a heating time of 10 minutes or less. Accordingly, the porous material can be produced not undergoing high-temperature treatment, and therefore its production is easy, and the production process has high reliability.
  • the material is used in formation of interlayer insulating films in production of semiconductor devices, it does not cause elongation of diffusion layers already formed or deterioration of wiring layers, and therefore semiconductor devices of high reliability can be provided.
  • the skeleton-forming crosslinkable material (a) may be an alkoxysilane, and the step of crosslinking the crosslinkable material to form the skeleton phase may comprise condensing the alkoxysilane to form an inorganic silane compound phase. Accordingly, a strong porous material of high reliability can be formed, which is resistant to acid and base.
  • the heat-decaying material (b) may have an oxygen atom content of from 15 to 55% by mass and at least 95% by weight of the material decays within 10 minutes when heated at a predetermined temperature falling between 150 and 350° C. Accordingly, in production of semiconductor devices, the material can be used not deteriorating element regions and wirings.
  • the polyoxyalkylene resin may have a number-average molecular weight of from 5000 to 5,000,000. Therefore, the heat-decaying material (b) is not so much volatile and can be handled more stably. In addition, rapid decaying of the material can be ensured.
  • the amount of the heat-decaying material (b) to be used may be from 5 to 1000 parts by weight relative to 100 parts by weight of the skeleton-forming crosslinkable material (a). Accordingly, the porous material produced has a low dielectric constant and a sufficient mechanical strength.
  • the precursor may be a composite prepared through partial hydrolysis condensation of the skeleton-forming crosslinkable material (a), and the composite is applied onto the substrate to be processed and then this is heated. Accordingly, forming the porous material on semiconductor substrates may be extremely readily realized.
  • the substrate to be processed may be a semiconductor substrate with semiconductor elements formed thereon, and the porous material may be formed as an interlay insulating film between the wiring layers that connect the semiconductor elements. Accordingly, interlayer insulating films having a low dielectric constant and having a high mechanical strength can be formed.
  • the heating of the precursor may be effected in two stages, a first heating, and a second heating at a temperature higher than the temperature in the first heating. Accordingly, the heat-decaying material may be decayed little by little first at low temperatures and then it may be decayed at a higher speed at higher temperatures. In that manner, more uniform porous materials may be formed.
  • the porous material obtained according to the above-mentioned production step is homogeneous and may have a high mechanical strength.
  • the porous material may be a porous film, and when the porous film is used as interlayer insulating films in electronic parts, the films have a low dielectric constant and have a high mechanical strength.
  • the transfer sheet of the invention has a transfer object stuck onto a heat-decaying adhesive resin layer. Accordingly, after the transfer object is transferred, the heat-decaying adhesive resin layer may be readily decayed merely by heating it.
  • the conductive particles transfer sheet that comprises the transfer sheet of the invention has conductive fine particles adhered to and disposed on a heat-decaying adhesive resin sheet. Accordingly, this enables connection with no mispositioning.
  • the conductive fine particles may be embedded in the heat-decaying adhesive resin sheet from its top face toward its back face. Accordingly, when a semiconductor chip or a semiconductor wafer is laid on one face of the conductive particles transfer sheet and when one face of the conductive fine particles is kept in contact with the electrode pad of the semiconductor chip or the semiconductor wafer and this is heated at the melting temperature of the surface of the conductive fine particles, then the conductive fine particles are fixed to the electrode pad and the heat-decaying resin is decayed. In that manner, connection of the conductive fine particles to the electrode pad with no mispositioning can be realized.
  • the conductive fine particles may be for bump-bonding between electrodes of an electronic part, and the particles are melt-bonded on the electrodes. Accordingly, this enables easy connection only by heating, not using a bonding agent such as solder.
  • the electronic part may be a semiconductor chip, a resin-encapsulated semiconductor device or a wiring board.
  • the transfer sheet enables easy bump formation on semiconductor chips, resin-encapsulated semiconductor devices or wiring boards with no mispositioning.
  • the conductive fine particles may have solder at least on their surface. With that, the particles may be fused and bonded only by heating.
  • the conductive fine particles may form solder ball bumps in BGA packages.
  • the transfer sheet enables easy formation of solder ball bumps with no mispositioning.
  • the conductive fine particles may from bumps on semiconductor chips.
  • the transfer sheet enables bump formation with no mispositioning.
  • the heat-decaying adhesive resin may contain a polyoxyalkylene resin. Accordingly, the conductive particles transfer sheet may be removed at low temperatures not leaving any residue after its removal.
  • the heat-decaying adhesive resin may be formed of a coating film that contains a polyalkylene resin composition. Accordingly, positioning and fixation of the conductive fine particles is easy.
  • the heat-decaying adhesive resin may give a more volatile residue when decomposed under reduced pressure. In that condition, therefore, the decomposition residue may be reduced.
  • the adhesive resin is decayed under heat at a predetermined temperature falling between 150 and 350° C. under reduced pressure within 5 minutes, then the heating time may be shortened. Accordingly, even conductive fine particles that are readily damaged by heat can be used in the transfer sheet.
  • the method of the invention for bonding conductive fine particles to the electrode face of electronic parts comprises attaching a conductive particles transfer sheet to electronic parts where conductive fine particles are disposed on the heat-decaying adhesive sheet in such a manner that the conductive fine particles could be in contact or in no contact with the position of the electrodes of the electronic parts, then melting and bonding the conductive fine particles to the electrodes of the electronic parts, and heating the resulting structure to decay the heat-decaying adhesive sheet.
  • connection can be realized with good positional accuracy and with good operability.
  • the method of the invention for bonding conductive fine particles to electrodes comprises casting a paste of the heat-decaying material on the surface of electronic parts with electrode face formed thereon, to thereby form a heat-decaying resin layer on them, disposing and bonding conductive fine particles to the electrode face via the heat-decaying resin layer, then melting and bonding the conductive fine particles to the electrodes of the electronic parts, and heating the resulting structure to decay the heat-decaying adhesive sheet.
  • connection can be realized with good positional accuracy and with good operability.
  • the method of the invention for bonding conductive fine particles to electrodes comprises applying a solution that contains a composition of the heat-decaying material to the surface of electronic parts with electrode face formed thereon, forming a heat-decaying resin layer from the coating film, disposing and bonding conductive fine particles to the electrode face via the heat-decaying resin layer, then melting and bonding the conductive fine particles to the electrodes of the electronic parts, and heating the resulting structure to decay the heat-decaying adhesive sheet.
  • connection can be realized with good positional accuracy and with good operability.
  • a solution that contains the heat-decaying adhesive resin composition may be applied to form the coating film, and then the coating film is exposed to UV ray to form the heat-decaying resin layer. Accordingly, in the method, pattern formation can be attained through exposure to light in the method, and therefore electrode patterning can be attained with no use of photoresist.
  • recesses may be formed in a predetermined region of the heat-decaying adhesive sheet or the heat-decaying resin layer through exposure to laser rays, and the conductive fine particles may be bonded to and disposed in the recesses.
  • the conductive fine particles may be bonded to and disposed in the recesses that are formed in a predetermined region of the heat-decaying adhesive sheet or the heat-decaying resin layer through exposure to laser rays. Accordingly, in the method, the conductive fine particles may be stably bonded to the predetermined region of the heat-decaying sheet or the heat-decaying resin layer.
  • the electronic parts may be semiconductor chips, resin-encapsulated semiconductor devices or wiring boards. Accordingly, the method enables easy bump formation.
  • the conductive fine particles may have solder on at least their surface. Accordingly, in the method, bonding of the heat-decaying material may be realized by solder-bonding the conductive fine particles.
  • the conductive fine particles may have solder on at least their surface, and the melt-bonding of the conductive fine particles and the decaying of the heat-decaying adhesive sheet or the heat-decaying adhesive resin may be simultaneously effected under heat at a solder reflow temperature. Accordingly, in the method, bonding of conductive fine particles such as solder balls to substrates may be realized at the same time with the heating operation in the reflow step.
  • the transfer sheet of the invention may be a transfer sheet for circuit formation, and this loses its solid form when the heat-decaying material or the adhesive sheet comprising a heat-decaying material-containing composition therein is decomposed.
  • the adhesive sheet may be readily decomposed and decayed when heated. Therefore, the transfer sheet makes it easy to transfer a fine and high-density circuit pattern onto an insulating substrate and makes it possible to form a circuit board having fine and high-density wirings with high accuracy.
  • the solid form of the adhesive sheet changes under heat and the sheet thereby separates from the circuit pattern, the metal foil or the conductive paste layer.
  • the adhesive sheet When the adhesive sheet is formed of a composite film that partly contains the heat-decaying material, then the adhesive force of the adhesive sheet may be greatly lowered by the vapor generated through heat treatment to decompose the heat-decaying material, and as a result, the adhesive sheet can readily separate from the circuit pattern. Accordingly, it is easy to transfer a fine and high-density circuit pattern, a metal foil or a conductive paste onto an insulating substrate, and circuit boards having fine and high-density wirings can be formed with high accuracy.
  • the heat-decaying material contains a crosslinkable resin composition that may crosslink through energy stimulation thereto.
  • the crosslinkable resin composition may be crosslinked and cured through exposure to UV rays or electron rays.
  • the adhesive sheet does not require heat treatment for suitably curing it, and the absence of heat treatment in the curing step completely prevents the heat-decaying material from being decomposed. It is possible to obtain a transfer sheet for forming high-quality circuits.
  • the transfer sheet for circuit formation may contain a heat-decaying material resin that comprises a crosslinkable silyl group-having polyoxyalkylene resin, and the temperature for the above-mentioned heat treatment may be a relatively low temperature not higher than 200° C.
  • circuit boards having fine and high-density wirings can be produced in a simplified manner at high producibility and with high accuracy.
  • the heat-decaying material comprises a crosslinkable silyl group-having polyoxyalkylene resin, and the heating temperature is controlled to fall between 150° C. and 170° C. Accordingly, in production of circuit boards, the circuit boards being produced are not exposed to high temperatures for a long period of time, and the materials and the properties of the circuit boards produced are not negatively influenced at all by the production process. In addition, any large-scale heating equipment is unnecessary and any simple-structured heating equipment is enough. Further, in production of electronic parts for which the acceptable limit of the heating temperature in the heating treatment is relatively low, or that is, not higher than 200° C., there occurs no change in the properties of the electronic parts produced, and the heat-decaying material of the invention is extremely effective for their production.
  • the transfer parts are electronic parts. Accordingly, the transfer sheet makes it possible to adhere electronic parts to a predetermined region with high positional accuracy. For example, this is extremely effective for parts positioning in a process of packaging machine parts such as racks or pinions formed through MEMS (micro-electro-mechanical systems) or NEMS (nano-electro-mechanical systems) technology, or cantilevers or air bridges.
  • MEMS micro-electro-mechanical systems
  • NEMS nano-electro-mechanical systems
  • cantilevers or air bridges cantilevers or air bridges.
  • a heat-decaying adhesive resin layer is formed on a cantilever formed on a silicon wafer and when this is positioned relative to another silicon wafer with a semiconductor integrated circuit formed thereon and attached thereto, then an acceleration sensor can be formed with ease.
  • a heat-decaying adhesive resin layer is formed on the MEMS switch beam formed on a silicon wafer and when this is positioned relative to the GaAs wafer with a semiconductor integrated circuit and an electric machine filter formed thereon and attached thereto, then a receiver device can be formed with ease.
  • the patterning method of the invention does not require direct patterning of a resist pattern and resist development after exposure transfer that are both indispensable in conventional patterning with a resist film. Accordingly, the patterning method of the invention is significantly simplified and the patterning costs may be lowered.
  • the working efficiency in the patterning method of the invention is improved and the patterning cost is thereby reduced and, in addition, the invention realizes high-accuracy patterning technology.
  • patterning of various materials for use in production of semiconductor devices can be significantly simplified, and the production costs are greatly reduced.
  • FIG. 1 includes cross-sectional views of a process scheme of producing a semiconductor device that has an interlayer insulating film formed of the porous material of the invention.
  • FIG. 2 includes cross-sectional views of a process scheme of forming solder ball bumps for BGA package for explaining the application embodiment 1 of a conductive particles transfer sheet.
  • FIG. 3 includes a plan view and a cross-sectional view of a conductive particles transfer sheet for use in the application embodiment 2 of the conductive particles transfer sheet.
  • FIG. 4 is a cross-sectional view of one process step in formation of solder ball bumps in the application embodiment 2 of the conductive particles transfer sheet.
  • FIG. 5 includes cross-sectional views of a process scheme of forming bumps on a semiconductor wafer for explaining the application embodiment 3 of a conductive particles transfer sheet.
  • FIG. 6 includes cross-sectional views of a transfer sheet for circuit formation.
  • FIG. 7 includes cross-sectional views of a process scheme for producing a circuit board.
  • FIG. 8 includes cross-sectional views of a process scheme for producing another circuit board.
  • FIG. 9 includes cross-sectional views of a process scheme of forming rearranged wiring on semiconductor chips.
  • FIG. 10 includes cross-sectional views of a process scheme of producing a circuit board for explaining a prior art.
  • FIG. 11 includes cross-sectional views showing a process scheme of the first embodiment of pattern formation of the invention.
  • FIG. 12 includes cross-sectional views showing a process scheme of the second embodiment of pattern formation of the invention.
  • FIG. 13 includes cross-sectional views showing a process scheme of the third embodiment of pattern formation of the invention.
  • FIG. 14 includes cross-sectional views of a process scheme of pattern formation that follows the above-mentioned process.
  • FIG. 15 includes cross-sectional views of a part of a process scheme of the fourth embodiment of pattern formation of the invention.
  • FIG. 16 includes cross-sectional views of a process scheme of pattern formation for explaining a prior art.
  • FIG. 17 includes cross-sectional views of a process scheme of pattern formation that follows the above-mentioned process.
  • the heat-decaying material of the invention comprises a polyoxyalkylene resin as the principal ingredient thereof, and has an oxygen atom content of from 15 to 55% by mass, and when heated at a predetermined temperature falling between 150 and 350° C., at least 95% by weight of the material decays within 10 minutes.
  • the heat-decaying material of the invention may have a sheet form at room temperature, or may have a paste morphology at room temperature and, when exposed to light or the like, it may crosslink into a cured product.
  • the polyoxyalkylene resin in the heat-decaying material of the invention includes both an uncrosslinked one and a crosslinked one.
  • the polyoxyalkylene resin in the heat-decaying material of the invention includes polymers that contain segments of polyalkylene glycol or polyoxyalkylene.
  • the polyalkylene glycol includes, for example, polyoxypropylene glycol, polyoxyethylene glycol, polyoxytetramethylene glycol.
  • the polyoxypropylene content of the mixed resin is at least 50% by mass.
  • a mixed resin of solid polyoxyethylene glycol and/or polyoxytetramethylene glycol is preferably used in the decaying material of the invention, since the properties of the material may be broadly varied including non-adhesive hot-melt-type resin sheets and adhesive sheets.
  • polyoxyalkylene segments are meant to indicate segments each having at least two repetitive units of the following formula (1):
  • n indicates an integer of 1 or more;
  • R 1n and R 2n each represent an n'th substituent of one or more selected and from a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a hydroxyl group, a carboxyl group, an epoxy group, an amino group, an amido group, an ether group and an ester group.
  • the heat-decaying material of the invention could not be completely decayed under heat. Even when the segment that has at least two repetitive units of formula (1) does not have a crosslinking point and the resin is crosslinked with any other segment to be a gel resin, then it may be used in the heat-decaying material of the invention so far as the above-mentioned polyoxyalkylene segment exist between the crosslinking points.
  • the copolymer that includes the above-mentioned polyoxyalkylene segments may be processed with a chain extender so that the segments may be chain-wise liked together.
  • the polymer that contains the polyoxyalkylene segments includes, for example, polymethylene glycol (polyacetal), polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polybutylene glycol, and combinations of different types of these segments. It further includes polyurethanes, polyesters, polyamides and polyimides that may be obtained from these. It still includes vinyl-based polymers such as (meth)acrylic polymers and polystyrenes that have these polyoxyalkylene segments as the grafts thereof. Two or more different types of these resins may be combined for use herein.
  • the number-average molecular weight of the polyoxyalkylene resin is from 500 to 5,000,000. If the number-average molecular weight is smaller than 500, then the resin will be too volatile and, if so, the decaying material of the invention may be difficult to stably handle. On the other hand, if the number-average molecular weight is larger than 5,000,000, then the cohesion force of the resin may be good but the resin could not be rapidly decayed owing to its entangled effect.
  • the number-average molecular weight of the resin may be suitably determined depending on the use, the object and the service condition of the heat-decaying material of the invention.
  • the heat-decaying material of the invention may contain a decomposition promoter or a decomposition retardant whereby the decomposition rate and the decomposition temperature of the material could be suitably controlled in accordance with the use, the object and the service condition of the material.
  • the decomposition promoter includes azo compounds such as azodicarbonamide; heavy metal compounds such as iron sulfate, sodium nitrate, cobalt naphthenate; carboxylic acids such as oxalic acid, linolenic acid, ascorbic acid; and hydroquinone, peroxides, tin oxide.
  • azo compounds such as azodicarbonamide
  • heavy metal compounds such as iron sulfate, sodium nitrate, cobalt naphthenate
  • carboxylic acids such as oxalic acid, linolenic acid, ascorbic acid
  • hydroquinone peroxides, tin oxide.
  • the peroxides are not specifically defined, and may be any of inorganic peroxides or organic peroxides. Concretely, they inorganic peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, potassium perchlorate, sodium perchlorate, ammonium perchlorate, and potassium periodate.
  • the organic peroxides are preferably those having a 10-hour half-value temperature of not lower than 100° C. when the heat-decaying material of the invention is desired to have good storage stability.
  • hydroperoxides such as p-menthanehydroxyperoxide, diisopropylbenzenehydroxyperoxide, 1,1,3,3-tetramethylbutylhydroxyperoxide, cumemehydroxyperoxide, t-hexylhydroxyperoxide, t-butylhydroxyperoxide; dialkylperoxides such as dicumylperoxide, ⁇ , ⁇ ′-bis (t-butylperoxy-m-isopropylbenzene), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumylperoxide, di-t-butylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3; peroxyketals such as 1,1-bis (t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cycl
  • the azo compounds include azobisisobutyronitrile (AIBN), 2,2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis(2-cyclopropylpropionitrile), 2,2-azobis(2-methylbutyronitrile), 1,1-azobis(cyclohexane-1-carbonitrile).
  • AIBN azobisisobutyronitrile
  • 2,2-azobis(2-cyclopropylpropionitrile) 2,2-azobis(2-methylbutyronitrile)
  • 1,1-azobis(cyclohexane-1-carbonitrile 1,1-azobis(cyclohexane-1-carbonitrile).
  • the heat-decaying material of the invention may reduce its carbide residue that may remain after thermally decayed.
  • the peroxides especially preferred are organic peroxides as more effective for reducing the generation of ash residues.
  • the decomposition retardant includes mercapto compounds, amine compounds, organic tin, organic boron.
  • the mercapto compounds include propanethiol, butanethiol, pentanethiol, 1-octanethiol, dodecanethiol, cyclopentanethiol, cyclohexanethiol, 1,3-propanediol.
  • the amine compounds include propylamine, butylamine, hexylamine, dodecylamine, isopropylamine, hexamethylenediamine, cyclohexylamine, benzylamine, aniline, methylaniline.
  • the organic tin includes dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin diacetate, dibutyltin-bis(2,4-pentanedione), dilauryltin dilaurate.
  • the organic boron includes trimethyl borate, tripropyl borate, tributyl borate, trimethoxyboroxine, trimethylene borate.
  • the amount of the decomposition promoter and the decomposition retardant in the heat-decaying material of the invention is not specifically defined and may be suitably determined depending on the use, the object and the service condition of the material. Concretely, it is desirable that the additive content is from 1 to 10% by mass of the heat-decaying material.
  • the heat-decaying material of the invention decays, when heated in an oxygen-containing atmosphere at a predetermined temperature falling between 150 and 300° C., or when heated in an anaerobic atmosphere at a predetermined temperature falling between 150 and 350° C., or when heated under reduced pressure within 5 minutes at a predetermined temperature falling between 150 and 350° C.
  • the decomposition temperature range of the material varies. Taking advantage of the properties thereof, the material may be used for various applications.
  • the heat-decaying material of the invention may have a sheet form, and the invention provides such a heat-decaying sheet.
  • the polyoxyalkylene resin to be in the heat-decaying material of the invention has a number-average molecular weight of from 5000 to 5,000,000.
  • the material may keep a stable sheet form at a temperature not lower than 100° C.; and when it is at most 5,000,000, then the cohesion force of the resin is not so high and its wettability does not decrease, and the resin-containing material may ensure a sufficient adhesive force.
  • the sheet may be reinforced with a substrate, or may not be reinforced with a substrate.
  • the material of the type is preferably reinforced with a substrate.
  • the material may be a supported-type sheet that is reinforced with a heat-resistant resin sheet such as; polyethylene terephthalate sheet or polyimide sheet, or with a substrate of metal film or the like.
  • a copolymer having polyalkylene glycol or polyoxyalkylene segments may be infiltrated into paper, plastics or woven or nonwoven fabrics of a glass material or the like so as to keep the sheet form of the material.
  • many of the polymers that contains polyoxyalkylene segments are also soft and could not keep a sheet form by themselves, it is also desirable that they are reinforced with a substrate so as to keep the sheet form thereof.
  • crosslinking morphology of the crosslinked polyoxyalkylene resin is not specifically defined, and it may be either physical crosslinking or chemical crosslinking.
  • a method of selecting crystalline segments for polymerization followed by crystallizing them there may be employed a method of using high-molecular-weight segments to increase entanglements of molecular chains; and a method of using segments having a functional group such as hydroxyl group, amino group or amido group to thereby form hydrogen bonding.
  • a crosslinkable functional group-having polymer that includes crosslinkable functional group-having polyalkylene glycol or polyoxyalkylene segments, with a crosslinking agent.
  • the crosslinkable functional group that the above-mentioned polyalkylene glycol or polyoxyalkylene segments-containing polymer has is not specifically defined, including, for example, a hydrolyzing silyl group, an isocyanate group, an epoxy group, an oxetanyl group, an acid anhydride group, a carboxyl group, a hydroxyl group, and a polymerizable unsaturated hydrocarbon group.
  • a hydrolyzing silyl group preferred is at least one selected from a hydrolyzing silyl group, an isocyanate group, an epoxy group, an oxetanyl group, an acid anhydride group, a carboxyl group, a hydroxyl group, and a polymerizable unsaturated hydrocarbon group; more preferred is at least one selected from a hydrolyzing silyl group, an epoxy group, and an oxetanyl group; and even more preferred is a hydrolyzing silyl group.
  • One or more different types of these crosslinkable functional groups may be in the polymer, either alone or as combined.
  • Some types of the polymer that contains hydrolyzing silyl group-having polyalkylene glycol or polyoxyalkylene segments are commercially available. For example, they are Kanegafuchi Chemical Industry's trade name MS Polymer Series of MS-Polymer-S-203, S-303, S-903; Silyl Polymer Series of Silyl SAT-200, MA-403, MA-447; Epion Series of EP103S, EP303S, EP505S; and Asahi Glass' Exsester ESS-2410, ESS-2420, ESS-3630.
  • the polymer that contains isocyanate group-having polyalkylene glycol or polyoxyalkylene segments may be obtained, for example, through urethanation of a diisocyanate such as 1,6-hexamethylene diisocyanate, TDI or MDI with polypropylene glycol in such a condition that the isocyanate amount by mol is larger than the hydroxyl amount by mol.
  • a diisocyanate such as 1,6-hexamethylene diisocyanate, TDI or MDI
  • polymers that contains epoxy group-having polyalkylene glycol or polyoxyalkylene segments are commercially available. For example, they are Kyoeisha Chemical's Epolite Series.
  • the polymerizable unsaturated hydrocarbon group includes a (meth)acryloyl group and a styryl group.
  • the polymer that contains the polymerizable unsaturated group e.g., (meth)acryloyl, styryl)-having polyalkylene glycol or polyoxyalkylene segments include, for example, ⁇ , ⁇ -di(meth)acryloyloxypolypropylene glycol, ⁇ , ⁇ -di(meth)acryloyloxypolyethylene glycol, ⁇ -(meth)acryloyloxypolypropylene glycol, ⁇ -(meth)acryloyloxypolyethylene glycol.
  • crosslinking agent to be used for the chemical crosslinking is described below.
  • the crosslinking agent for use in the chemical crosslinking may be any one having the ability to crosslink crosslinkable functional groups of polymers.
  • it is a type capable of reacting with the crosslinkable functional group of the above-mentioned polyalkylene glycol or polyoxyalkylene segments-having polymer capable being taken into the structure of the crosslinked product by itself (hereinafter this is referred to as crosslinking agent (1)); or a type capable of acting as a catalyst for the reaction of the crosslinkable functional groups that the polyalkylene glycol or polyoxyalkylene segments-containing polymer has (hereinafter this is referred to as crosslinking agent (2)).
  • Another type having both the function of the crosslinking agent (1) and the function of the crosslinking agent (2) is also usable herein, and this is referred to as crosslinking agent (3).
  • crosslinking agent (1) includes the following:
  • a crosslinking agent capable of crosslinking the polymer that contains oxetanyl group-having polyalkylene glycol or polyoxyalkylene segments includes an optical cationic initiator that generates an acid through exposure to UV rays or visible rays, and a thermal cationic initiator.
  • a crosslinking agent capable of crosslinking the polymer that contains isocyanate group-having polyalkylene glycol or polyoxyalkylene segments includes a compound having plural active hydrogens, such as a compound having plural hydroxyl groups or a compound having plural amino groups.
  • the compound having plural hydroxyl groups are, for example, ethylene glycol, butyleneglycol, glycerin, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, pentaerythritol, polyester-polyol.
  • the compound having plural amino groups are, for example, hexamethylene diamine, tetramethylenediamine, ⁇ , ⁇ -diaminopropylene glycol.
  • crosslinking agent (2) is not also specifically defined, concretely including the following:
  • the crosslinking agent capable of crosslinking the above-mentioned hydrolyzing silyl group includes, for example, a photoreactive catalyst having a functional group of the following formula (2), an optical cationic initiator capable of generating an acid through exposure to UV rays or visible rays, an organic metal compound, an amine compound, an acid phosphate, a tetraalkylammonium halide (halide includes fluoride, chloride, bromide, iodide), a carboxyl group having organic acid, and an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid.
  • m indicates an integer of from 2 to 5;
  • Y(m) represents an atom of Group IVB, VB or VIB of the Periodic Table;
  • Z represents a hydroxyl group, a hydrocarbon group, a mercapto group, an amino group, a halogen group, an alkoxyl group, an alkylthio group, a carbonyloxy group, or an oxo group.
  • the photoreactive catalyst having the functional group of formula (2) may have two or more different types of the functional groups of formula (2).
  • the functional group of formula (2) includes, for example, those derived from a compound having two carboxyl groups bonded to the atom of Y (m) that is selected from, for example, a group consisting of oxygen, sulfur, nitrogen, phosphorus and carbon, and suitably having a hydrocarbon group or an oxide group of Z in accordance with the number of atomic valences of Y(m).
  • the hydrocarbon group includes, for example, an aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, and an aromatic hydrocarbon group. These hydrocarbon groups may have a substituent of, for example, an amino group, a hydroxyl group, an ether group, an epoxy group, a polymerizable unsaturated group, an urethane group, an urea group, an imido group and an ester group, not interfering with the object of the invention. As the case may be, different types of hydrocarbon groups may be combined for use herein.
  • the photoreactive catalyst having a functional group of formula (2) may be a cyclic compound.
  • the cyclic compound is, for example, a compound having one or more different types of functional groups of formula (2) in the cyclic chain thereof.
  • a compound constructed by bonding plural and the same or different cyclic compounds to each other with a suitable organic group; and a twin-ring compound containing at least one or more units of plural and the same or different cyclic compounds as above, are also usable herein.
  • the photoreactive catalyst having a functional group of formula (2), in which the atom of Y(m) is an oxygen atom includes, for example, acetic acid anhydride, propionic acid anhydride, butyric acid anhydride, isobutyric acid anhydride, valeric acid anhydride, 2-methylbutyric acid, trimethylacetic acid anhydride, hexanoic acid anhydride, heptanoic acid anhydride, decanoic acid anhydride, lauric acid anhydride, myristic acid anhydride, palmitic acid anhydride, stearic acid anhydride, docosanoic acid anhydride, crotonic acid anhydride, acrylic acid anhydride, methacrylic acid anhydride, oleic acid anhydride, linolenic acid anhydride, chloroacetic acid anhydride, iodoacetic acid anhydride, dichloroacetic acid anhydride, trifluoroacetic acid anhydride,
  • Adeka Hardener EH-700 Adeka Hardener EH-703, Adeka Hardener EH-705A: Shin-Nippon Rika's Rikacid TH, Rikacid HT-1, Rikacid HH, Rikacid MH-700, Rikacid MH-700H, Rikacid MH-700H, Ricacid MH, Ricacid SH, Rikares in TMEG; Hitachi Kasei's HN-5000, HN-200; Yuka Shell Epoxy's Epicure 134A, Epicure YH306, Epicure YH307, Epicure YH308H; Sumitomo Chemical's Sumicure MS.
  • the photoreactive catalyst having a functional group of formula (2), in which the atom of Y(m) is a nitrogen atom includes, for example, succinimide, N-methylsuccinimide, ⁇ , ⁇ -dimethyl- ⁇ -methylsuccinimide, ⁇ -methyl- ⁇ -propylsuccinimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(2-chlorophenyl)maleimide, N-benzylmaleimide, N-(1-pyrenyl)maleimide, 3-methyl-N-phenylmaleimide, N,N7-1,2-phenylenedimaleimide, N,N′-1,3-phenylenedimaleimide, N,N′-1,4-phenylenedimaleimi
  • the photoreactive catalyst having a functional group of formula (2), in which the atom of Y (m) is a phosphorus atom, includes, for example, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoylphenylphosphine oxide.
  • the photoreactive catalyst having a functional group of formula (2), in which the atom of Y(m) is a carbon atom includes, for example, diketones such as 2,4-pentanedione, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3-chloro-2,4-pentanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1-benzoylacetone, dibenzoylmethane; polycarboxylates such as dimethyl malonate, diethyl malonate, dimethyl methylmalonate, tetraethyl 1,1,2,2-ethanetetracarboxylate; and ⁇ -carbonyl-acetates such as methyl acet
  • photoreactive catalysts having a functional group of formula (2) especially preferred are diacylphosphine oxides and their derivatives as their residue to remain after decay is extremely small.
  • the amount of the photoreactive catalyst having a functional group of formula (2) that may be in the material of the invention is preferably from 0.01 parts by weight to 30 parts by weigh as the uppermost limit, relative to 100 parts by weight of the polymer that contains the hydrolyzing silyl group-having polyalkylene glycol or polyoxyalkylene segments.
  • the catalyst could not exhibit photoreactivity; but if larger than 30 parts by weight, then the light transmittance of the composition that contains the polymer having hydrolyzing silyl group-having polyalkylene glycol or polyoxyalkylene segments may lower, and, if so, even when the composition is exposed to light, only the surface part thereof could be crosslinked and cured but the depth thereof could not be crosslinked and cured. More preferably, the lowermost limit of the content is 0.1 parts by weight; and the uppermost limit thereof is 20 parts by weight.
  • the organic metal compound includes, for example, tin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate)oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester maleate), tin octylate, dibutyltin octanoate, dioctyltin oxide; and alkyloxy titanates such as tetra-n-butoxy titanate, tetraisopropoxy titanate.
  • tin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis(dibutyltin laurate)oxide, dibutyltin bisacetylacetonate, dibutyltin bis (
  • the crosslinking agent for crosslinking the polymer that contains the above-mentioned polymerizable unsaturated group-having polyalkylene glycol or polyoxyalkylene segments includes, for example, thermal radical initiators such as peroxides, azo compounds; optical radical initiators that act through exposure to UV rays or visible rays; and combined initiator systems comprising a thermal or optical radical initiator and a compound having plural mercapto groups.
  • the thermal radical initiator includes, for example, hydroperoxides such as diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumeme hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide; dialkyl peroxides such as ⁇ , ⁇ ′-bis(tert-butylperoxy-m-isopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3; organic peroxides such as ketone peroxides, peroxy ketals, diacyl peroxides, peroxy dicarbonates, peroxy esters; and azo compounds such as 2,
  • the optical radical initiator includes, for example, acetophenone derivative compounds such as 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ ′-dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone; benzoin ether compounds such as benzoin ethyl ether, benzoin propyl ether; ketal derivative compounds such as benzyldimethyl ketal; halogenoketones; acylphosphine oxides; acyl phosphates; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-N,N-dimethylamino-1-(4-morphoinophenyl)-1-butanone; bis(2,4,6-trimethylbnzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)
  • the crosslinking agent that crosslinks the polymer having the above-mentioned epoxy group-containing polyalkylene glycol or polyoxyalkylene segments includes, for example, an optical cationic initiator capable of generating an acid through exposure to UV rays or visible rays, a thermal cationic initiator, an amine compound-type curing agent, an amide-type curing agent, an acid anhydride-type curing agent, a mercapto-type curing agent, a thermal latent curing agent such as ketimine or DICY, and an optical amine generator having a carbamoyloxyimino group or the like.
  • the optical cationic catalyst includes, for example, iron-arene complex compounds, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, pyridinium salts, aluminium complex/silanol salts, trichloromethyltriazine derivatives.
  • onium salts and pyridinium salts for example, SbF 6 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , BF 4 ⁇ tetrakis(pentafluoro)borate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, acetate, sulfonate, tosylate, nitrate.
  • optical catalysts are commercially available, for example, Irgacure 261 (by Ciba-Geigy), Optomer SP-150 (by Asahi Denka Kogyo), Optomer SP-151 (by Asahi Denka Kogyo), Optomer SP-170 (by Asahi Denka Kogyo), Optomer sP-171 (by Asahi Denka Kogyo), UVE-1014 (by General Electronics), CD-1012 (by Sartomer), Sunaid SI-60L (by Sanshin Chemical Industry), Sunaid SI-80L (by Sanshin Chemical Industry), Sunaid SI-100L (by Sanshin Chemical Industry), CI-2064 (by Nippon Soda), CI-2639 (by Nippon Soda), CI-2624 (by Nippon Soda), CI-2481 (by Nippon Soda), RHODORSIL PHOTOINITIATOR 2074 (by Rhone-Poulenc), UVI-6990 (by Rh
  • the thermal cationic curing agent includes, for example, ammonium salts, sulfonium salts, iodonium salts and diazonium salts each having at least one alkyl group, as well as boron trifluoride/triethylamine complex.
  • the counter anion of these salts include, for example, anions such as SbF 6 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , BF 4 ⁇ tetrakis(pentafluoro)borate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, acetate, sulfonate, tosylate, nitrate.
  • the optical amine generator includes, for example, carbamoyloxyimino group-having compounds, cobalt-amine complexes, o-nitrobenzyl carbamate, o-acyloximes.
  • the crosslinking agent (3) is not specifically defined, and is, for example, ⁇ , ⁇ -diaminopolyoxypropylene.
  • the heat-decaying material of the invention which contains a crosslinked polyoxyalkylene resin and therefore has a form of a heat-decaying sheet, may contain a functional group-having compound that is derived from the same reaction intermediate as that for the polymer that has crosslinkable functional group-having polyalkylene glycol or polyoxyalkylene segments, as a copolymerizable or co-crosslinkable component, not interfering with object of the invention.
  • It may also contain a crosslinkable or polymerizable functional group-having compound that is derived from a reaction intermediate differing from that for the polymer that has crosslinkable functional group-having polyalkylene glycol or polyoxyalkylene segments, as a copolymerizable or co-crosslinkable component. Further, it may contain a compound having both these two types of functional groups.
  • the copolymerizable or co-crosslinkable component includes, for example, radical polymerizable unsaturated group-having compounds.
  • the radical polymerizable unsaturated group-having compounds are, for example, styryl group-having compounds such as styrene, indene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene; and (meth)acryloyl group-having compounds such as methyl (meth)acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (
  • the copolymerizable or co-crosslinkable component further includes, for example, epoxy group-having compounds.
  • epoxy group-having compounds are, for example, bisphenol A-type epoxy resins, hydrogenated bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, novolak-type epoxy resins, cresol-type epoxy resins, aliphatic cyclic epoxy resins, bromoepoxy resins, rubber-modified epoxy resins, urethane-modified epoxy resins, glycidyl ester-type compounds, epoxydated polybutadiene, epoxydated SBS (SBS indicates poly(styrene-co-butadiene-co-styrene) copolymer).
  • the copolymerizable or co-crosslinkable component further includes, for example, isocyanate group-having compounds.
  • isocyanate group-having compounds are, for example, xylylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, 1,6-hexamethylene diisocyanate, phenylmethane diisocyanate.
  • the heat-decaying material of the invention which contains a crosslinked polyoxyalkylene resin and therefore has a form of a heat-decaying sheet, may be a non-supported type with no substrate, or may be a supported type that comprises a layer of a polymer containing polyalkylene glycol or polyoxyalkylene segments formed on one or both faces of a substrate processed or not processed for lubrication.
  • the heat-decaying material of the invention which contains an uncrosslinked or crosslinked polyoxyalkylene resin and has a form of a heat-decaying sheet, may be controlled to have broad-range properties to be adhesive or non-adhesive.
  • polypropylene glycol is the principal component of the material
  • the material may be highly adhesive; but when the content of solid polyethylene glycol or polytetramethylene glycol in the material is higher, then the adhesiveness of the material may lower. Further, the adhesiveness of the material may be controlled depending on the crosslinking degree of the resin in the material.
  • the method for producing the heat-decaying material of the invention which has a form of a heat-decaying sheet is not specifically defined.
  • the material may be formed in any known method, for example, of solvent casting, extrusion coating, calendering or UV polymerization in coating.
  • the heat-decaying material of the invention which has a form of a heat-decaying sheet is produced according to a solvent casting process
  • the starting resin and optionally additives such as crosslinking agent and filler are dissolved or dispersed in a solvent
  • the resulting solution is cast onto a lubrication-processed film, and the solvent is removed by drying.
  • the heat-decaying material of the invention which has a form of a heat-decaying sheet is produced according to a hot-melt coating process
  • the starting resin and optionally additives such as crosslinking agent and filler are mixed and dispersed under heat, and then applied onto a substrate through a T-die or the like in a mode of hot-melt coating.
  • the heat-decaying material of the invention which has a form of a heat-decaying sheet is produced according to a process of UV polymerization in coating, for example, a composition prepared by mixing a photo-crosslinkable functional group-having starting resin, an initiator or a crosslinking agent selected in accordance with the crosslinkable functional group, and optionally various additives such as filler is applied to a substrate while exposed to light capable of activating the optical initiator.
  • the lamp for light irradiation includes, for example, low-pressure mercury lamp, middle-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp.
  • the wavelength range light may be cut off through a suitable filter before light irradiation.
  • a sensitizer may be previously added to the starting composition.
  • the sensitizer includes, for example, anthracene derivatives, thioxanthone derivatives.
  • the heat-decaying material of the invention which has a form of a heat-decaying sheet is produced according to a thermal polymerization process
  • a composition prepared by mixing a thermal-crosslinkable functional group-having starting resin, an initiator or a crosslinking agent selected in accordance with the crosslinkable functional group, and optionally various additives such as filler is applied to a substrate while heating it to polymerize or crosslink the resin.
  • the heating method in this case includes, for example, hot plate, hot press, drying oven, heat gun, IR heater, dielectric heater, induction heater, ultrasonic heater.
  • the resin to be crosslinked has multiple crosslinkable functional groups that differ depending on their object, then plural production methods may be combined for the resin.
  • the heat-decaying material of the invention may have a paste morphology at room temperature, and it may be crosslinked through exposure to light into a cured product (this may be hereinunder referred to as a paste-type heat-decaying material).
  • a paste-type heat-decaying material The material of this type is described below.
  • the paste-type heat-decaying material of the invention comprises a polymer that contains crosslinkable functional group-having polyoxyalkylene glycol or polyoxyalkylene segments and a crosslinking agent, and its viscosity at 20° C. falls between 1 and 5,000,000 mPa•s.
  • the polymer that contains polyoxyalkylene glycol or polyoxyalkylene segments, the crosslinkable functional group that the polymer has, and the crosslinking agent to be in the paste-type heat-decaying material of the invention may be the same as those mentioned hereinabove.
  • the number-average molecular weight of the crosslinkable functional group-having polymer that contains crosslinkable functional group-having polyoxyalkylene glycol or polyoxyalkylene segments is preferably at most 5000.
  • the paste-type heat-decaying material of the invention contains at most 30% by mass of a polymerizable unsaturated group-having compound, then its curability may be enhanced.
  • the polymerizable unsaturated group of the polymerizable unsaturated group-having compound is not specifically defined, including, for example, a styryl group, an acryloyl group, a methacryloyl group, a vinyl ester group, a vinyloxy group.
  • the styryl group-having compound includes, for example, styrene, indene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene.
  • the acryl group or methacryloyl group-having compound includes, for example, methyl (meth)acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (me
  • the vinyl ester group-having compound includes, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate.
  • the vinyloxy group-having compound includes, for example, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, (4-vinyloxy)butyl benzoate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol divinyl ether, hexane-1,6-diol divinyl ether, cyclohexane-1,4-dimethanol divinyl
  • the viscosity of the paste-type heat-decaying material of the invention may fall between 1 and 5,000,000 mPa•s at 20° C., but may be suitably selected and determined depending on the use, the object and the service condition of the material.
  • the viscosity of the material at 20° C. preferably falls between 1 and 100 mPa•s.
  • the viscosity of the material at 20° C. preferably falls between 500 and 100,000 mPa•s.
  • the viscosity of the material at 20° C. preferably falls between 20 and 1,000 mPa•s.
  • the paste-type heat-decaying material of the invention keeps its paste condition at room temperature, having a viscosity at 20° C. falling between 10 and 5,000,000 mPa•s, but when it receives energy for crosslinking, then it crosslinks and cures into a crosslinked and cured product.
  • the polyoxyalkylene resin in the paste-type heat-decaying material of the invention may be decomposed and lost if overheated, and therefore some attention must be paid thereto.
  • photocrosslinking is preferred for crosslinking and curing the paste-type heat-decaying material of the invention.
  • the lamp for light irradiation includes, for example, low-pressure mercury lamp, middle-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp.
  • the wavelength range light may be cut off through a suitable filter before light irradiation.
  • a sensitizer may be added to the heat-decaying material.
  • the sensitizer includes, for example, anthracene derivatives and thioxanthone derivatives.
  • the paste-type heat-decaying material of the invention is thermally crosslinked and cured
  • employable are a method and an apparatus for heating the heat-decaying material.
  • the method and the apparatus in this case include, for example, hot plate, hot press, drying oven, heat gun, IR heater, dielectric heater, induction heater, ultrasonic heater.
  • the crosslinkable functional group-having polymer that contains crosslinkable functional group-having polyoxyalkylene glycol or polyoxyalkylene segments may be partially crosslinked with a crosslinking agent so that the resulting material may have a micro-gel morphology.
  • the cured product obtained by crosslinking the paste-type heat-decaying material of the invention keeps the cured product form thereof at a temperature not higher than 100° C., but when heated at a predetermined temperature falling between 150 and 350° C., then at least 95% by weight of the cured product decays within 10 minutes.
  • the heat-decaying material of the invention may contain a liquid resin. Containing a liquid resin, the decay-initiating temperature of the heat-decaying material of the invention lay be lowered and the material may be rapidly decayed at 150° C. or higher.
  • the liquid resin may be any compound having a boiling point not lower than 100° C. in consideration of the shape sustainability of the heat-decaying sheet and the decaying temperature thereof. For example, it includes polyethylene glycol oligomer, polypropylene oligomer, polytetramethylene glycol oligomer, dioctylphthalate, dibutyl phthalate, glycerin monooleate.
  • the heat-decaying material of the invention may contain a filler such as titanium oxide, alumina, colloidal calcium carbonate, heavy calcium carbonate, barium carbonate, magnesium carbonate, silica, surface-processed silica, calcium silicate, anhydrous silicon, hydrous silicon, mica, surface-processed mica, talc, clay, surface-processed talc, boron nitride, alumina nitride, carbon nitride, carbon black, white carbon, short glass fibers, glass beads, glass balloons, shirasu balloons, acryl beads, polyethylene beads. Containing it, the cohesion force of the sheet or the cured product increases. However, since it inevitably gives an inorganic residue, its content must be the necessary minimum one.
  • the heat-decaying material of the invention may contain a silane coupling agent.
  • the silane coupling agent includes, for example, vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N′-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N′-bis[3-(triethoxysilyl)propyl]ethylenediamine, N
  • the heat-decaying material of the invention may contain a titanium coupling agent.
  • the titanium coupling agent includes, for example, isopropyl triisostearoyltitanate, isopropyl n-dodecylbenzenesulfonyltitanate, isopropyl tris(dioctylpyrophosphate)titanate, tetraisopropyl bis(dioctylphosphite)titanate, tetraisopropyl bis(ditridecylphosphite)titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyl tri(N-aminoethyl-aminoethyl)titanate.
  • the heat-decaying material of the invention may contain a adhesiveness-improving resin such as rosins, rosin esters, disproportionated rosin esters, hydrogenated rosin esters, polymerized rosin esters, terpene resins, terpene-phenol resins, aromatic modified terpene resins, C5/C9 petroleum resins, hydrogenated petroleum resins, phenol resins, chroman-indene resins, ketone resins, xylene resins, for the purpose of increasing the adhesiveness of the material.
  • a adhesiveness-improving resin such as rosins, rosin esters, disproportionated rosin esters, hydrogenated rosin esters, polymerized rosin esters, terpene resins, terpene-phenol resins, aromatic modified terpene resins, C5/C9 petroleum resins, hydrogenated petroleum resins, phenol resins, chroman-indene resins, ketone resins, xylene resin
  • the heat-decaying material of the invention may contain any of dropping inhibitor, antioxidant, antiaging agent, UV absorbent, solvent, fragrance, pigment and dye, in accordance with the use and the service mode of the material.
  • the heat-decaying material and its cured product of the invention are not specifically defined, provided that at least 95% by weight thereof could decay within 10 minutes when heated at a predetermined temperature falling between 150 and 350° C., but they may be suitably selected and prepared so that their decaying temperature could satisfy the use object and the service mode of the material.
  • the material when the material could decay in a temperature atmosphere falling between 150 and 220° C., then it may be used for temporary fixation and for other various applications since it may be decayed in a process of temporary fixation of optical parts or in a process of packaging semiconductor devices by the use of low-temperature solder.
  • the material When the material could decay in a temperature atmosphere falling between 220 and 280° C., then it may be used for temporary fixation and for other various applications since it may be decayed in a process of packaging semiconductor devices by the use of lead-free solder.
  • the material When the material could decay in a temperature atmosphere falling between 280 and 350° C., then it may be used in forming porous thin film on aluminium wiring and may be used for various applications.
  • the heat-decaying material and its cured product of the invention hardly decompose at a temperature not higher than 100° C. and keep their solid form, but may rapidly decompose at a relatively low temperature falling between 150 and 350° C. so that most of the solid part thereof decays. Accordingly, when heated, the material may be readily removed from the objects to which it has stuck, and, in addition, the objects receive little thermal influence.
  • the heat-decaying material of the invention can be used, for example, as a temporary fixer such as binder for temporary fixation of glass fibers, and, after used, the temporary fixation with it may be relieved by heating; or it may be used as an adhesive for fixation of interlayer film for glass laminates, plasma display heat-conductive sheets or wallpapers, for fixation of gravel on railways, for fixation of stone structures, and for fixation of gypsum boards, and when recycled, it may be recovered merely by heating with no damage to the structures; or it may be used in temperature sensors in such a manner that it is disposed between contact points or one contact point is fixed with it and it is decayed at a predetermined temperature so as to shut up the contact point; or it may be used as a fixation paste or a fixation sheet for temporarily fixing metal surface-protective sheets, rust-preventing covers or polished samples; or it may be used as an under film for reinforcing semiconductor chips or substrates, and, when desire, it may be removed by heating; or it may be used
  • the heat-decaying material of the invention is favorably used as a masking agent in working articles for preventing the area around the worked part of the articles from being soiled.
  • the masking agent of the type is favorably used in a masking material that covers the area to be processed, for example, in a process of etching substrates for electronic parts or chips of electronic parts through laser processing or in a process of forming through-holes.
  • a re-peelable adhesive tape is used for such a masking material.
  • the masking material of the re-peelable adhesive tape must be peeled after working.
  • the heat-decaying material of the invention when used as a masking material, then it can be readily removed by heating after working.
  • the heat-decaying material of the invention when so designed that it is transparent, and even when the masking material is applied so as to cover even the part to be worked, the covered structure could be worked with laser or the like. Accordingly, since the masking material may be applied to the region that includes the part to be worked and therearound, the working efficiency may be enhanced.
  • the heat-decaying material of the invention can be cast in the absence of solvent, it may be readily applied to the surface of the objects to be worked, as a masking material thereover.
  • porous films conductive particles transfer sheets mentioned above, transfer sheets for circuit formation, and pattern formation. These are described in detail hereinunder.
  • the method for producing a porous material comprises:
  • crosslinkable material for skeleton formation For forming the matrix of the porous material, used is a crosslinkable material for skeleton formation.
  • the crosslinkable material for skeleton formation is not specifically defined, but alkoxysilane is favorably used for it.
  • the alkoxysilane may be any type of alkoxysilane formed through condensation of an inorganic silane compound phase.
  • Preferred examples of the alkoxysilane of the type includes dimethoxydimethylsilane, cyclohexyldimethoxymethylsilane, diethyldimethylsilane, dimethoxymethyloctylsilane, diethoxymethylvinylsilane, chloromethyl(diisoprooxy)methylsilane, dimethoxymethylphenylsilane, diethoxydiphenylsilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, trimethoxypropylsilane, isobutyltrimethoxysilane, octyltrimethoxysilane, octadecyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,
  • the alkoxysilane condenses in the heating step that will be mentioned hereinunder, and forms an inorganic silane compound phase, or that is, an SiO 2 phase to constitute the matrix phase of a porous material.
  • the alkoxysilane is liquid at room temperature, and therefore, in the precursor that contains the alkoxysilane and the heat-decaying material (b) of the invention mentioned below, the heat-decaying material may be uniformly dispersed.
  • the heat-decaying material (b) of the invention is prepared, as dispersed or dissolved in the above-mentioned, skeleton-forming crosslinkable material (a), concretely, liquid alkoxysilane.
  • the heat-decaying material is dispersed and when the particle size thereof is controlled, then the size of the pores that are formed after the heat-decaying material has been decayed under heat may be thereby controlled. Accordingly, it is desirable that the particle size of the heat-decaying material is uniform.
  • the pore size must be satisfactorily large, for example, preferably falling between 0.01 ⁇ m and 100 ⁇ m or so. Accordingly, the particle size of the heat-decaying material is preferably from 0.01 ⁇ m to 100 ⁇ m or so.
  • the ratio of the heat-decaying material is preferably from 5 to 1000 parts by weight to 100 parts by weight of the skeleton-forming crosslinkable material (a). If the ratio is less than 5 parts by weight, then the porosity will be too low and the dielectric constant could not be sufficiently low; but if larger than 1000 parts by weight, then the strength of the porous material may lower.
  • the skeleton-forming crosslinkable material (a) and the heat-decaying material may be mixed in any suitable method, and the heat-decaying material may be thereby readily uniformly dispersed.
  • a precursor that comprises the heat-decaying material dispersed in the skeleton-forming crosslinkable material (a) is obtained in the manner mentioned above, and the precursor is heated at a temperature not lower than the temperature at which the heat-decaying material decays under heat. Accordingly, when the skeleton-forming crosslinkable material (a) is an alkoxysilane, then an inorganic silane compound phase is formed through condensation of the alkoxysilane and the heat-decaying material in the inorganic silane compound phase is decayed to give a large number of pores. Specifically, a porous material is thereby obtained in that manner.
  • the heating may be effected, for example, at a temperature falling between 150 and 350° C.
  • the pores may be formed by heating at a relatively low temperature.
  • the pores may be formed by heating at a temperature in the range within 10 minutes, or that is, a porous material can be obtained within a relatively short period of time.
  • the porous material thus obtained may be used for various applications. Specifically, since a large number of uniform and satisfactorily large pores are dispersed in the material and since the resulting porous material may have a high mechanical strength, the porous material may be favorably used as interlayer insulating films, as electrodes or proton-conductive films in fuel cells, and as heat-insulating materials. In particular, since relatively large pores can be uniformly dispersed therein, the porous film of the porous material can be favorably used as interlayer insulating films in electronic structures such as semiconductor devices or multi-layered substrates.
  • a conductive particles transfer sheet that comprises the heat-decaying material of the invention is described below.
  • the conductive particles transfer sheet that comprises the heat-decaying material of the invention is characterized in that conductive fine particles are adhered to and disposed on a sheet-type heat-decaying material.
  • Embodiments of the conductive particles transfer sheet that comprises the heat-decaying material of the invention are described in detail hereinunder.
  • Embodiment 1 of the conductive particles transfer sheet that comprises the heat-decaying material of the invention is described with reference to FIG. 2 .
  • FIG. 2 includes cross-sectional views of a process scheme of forming solder ball bumps for BGA package and connecting them to a mother board, wiring board by the use of the above-mentioned conductive particles transfer sheet. In this, semiconductor chips are mounted on the BGA package.
  • an antioxidant layer 13 is formed of Au foil or the like on the Cu wiring layer 12 formed in a BGA package 11 , and a flux 14 is applied to the antioxidant layer 13 to cover it.
  • a conductive particles transfer sheet 17 that comprises a heat-decaying adhesive sheet 15 and solder balls 16 adhered to predetermined regions of the surface thereof is laminated onto the BGA package 11 while the position of the Cu wiring layer 12 of the BGA package 11 is aligned with that of the solder ball 16 .
  • the heat-decaying adhesive sheet 15 is formed of a polyoxyalkylene resin having a thickness of 50 ⁇ m or so.
  • the solder ball 16 is formed of Pb—Sn alloy solder or Pb-free solder such as Sn—Cu, Sn—Ag or Sn—Zn solder, and its diameter is 500 ⁇ m or so.
  • solder-reflow heat treatment In an nitrogen atmosphere at a temperature falling between 200° C. and 250° C., this is subjected to solder-reflow heat treatment, and the solder balls 16 are thereby melt-fused to the Cu wiring layer 12 . In that manner, as in FIG. 2( c ), solder ball bumps 18 are formed on the Cu wiring layer 12 of the BGA package 11 . At the same time in the heat-treatment, the heat-decaying adhesive sheet 15 of the conductive particles transfer sheet 17 is pyrolyzed and vaporized, and is thereby completely decayed.
  • the Au atom of the antioxidant layer 13 melts in the solder ball bump 18 , and a semiconductor device 19 is thus formed in which semiconductor chips are mounted on the BGA package 11 that has the solder ball bumps 18 in predetermined regions.
  • the BGA package comprises a multi-level wiring board.
  • an electrode pad 111 of Cu on a wiring substrate, mother board 110 is melt-bonded to the solder ball bump 18 , and a semiconductor device 19 is thereby mounted on the mother board 10 .
  • a low-melting-point organic acid is added to the heat-decaying adhesive sheet 15 , then it acts to clean the surface of the Cu wiring layer 12 , and therefore, the flux 14 will be unnecessary.
  • the antioxidant layer 13 may be omitted.
  • Embodiment 2 a modification of Embodiment 1 of the conductive particles transfer sheet is described with reference to FIG. 3 and FIG. 4 .
  • the same parts as those in FIG. 2 are indicated by the same reference numerals.
  • the difference between Embodiment 2 and Embodiment 1 is that, in Embodiment 2, the solder balls 16 are embedded into the heat-decaying adhesive sheet 15 and is adhered and positioned therein in the conductive particles transfer sheet 17 described in FIG. 2( b ).
  • FIG. 3( a ) is a plan view of the conductive particles transfer sheet 17 ; and FIG. 3( b ) is a cross-sectional view of FIG. 3( a ) cut along X 1 -X 2 .
  • a large number of solder balls 16 are disposed in the heat-decaying adhesive sheet 15 .
  • the solder balls 16 are embedded and fitted into the heat-decaying adhesive sheet 15 , as in FIG. 3 ( b ) .
  • solder ball 16 adheres to the flux 14 at the bottom thereof.
  • this is subjected to heat treatment at a solder reflow temperature falling between 160° C. and 180° C. or so in a nitrogen atmosphere, whereby the solder balls 16 are melt-bonded to the Cu wiring layer 12 .
  • this is then heated in a nitrogen atmosphere at 200 to 250° C. whereby the heat-decaying adhesive sheet 15 of the conductive particles transfer sheet 17 is decayed.
  • the solder ball bumps 18 are formed on the Cu wiring layer 12 of the BGA package 11 , as in FIG. 2 ( c ) .
  • this is mounted on another board.
  • the heat-decaying adhesive sheet 15 does not exist below the bottom of each solder ball 16 in the solder reflow treatment step, different from that in the case of FIG. 2( b ), and therefore the melt-bonding can be attained within a shorter period of time with higher accuracy in this Embodiment 2.
  • the above-mentioned melt-bonding and decaying can be attained simultaneously through the same heat treatment as in the above-mentioned Embodiment 1.
  • FIG. 5 includes cross-sectional views of a process scheme of forming bumps on the surface of a semiconductor chip or semiconductor wafer.
  • a passivation film 122 of a silicon nitride or silicon oxynitride film is formed on the surface of a 8-inch ⁇ semiconductor wafer 121 with semiconductor elements and internal wiring (not shown) formed thereon, and an outer lead wiring 123 is formed on it.
  • the outer lead wiring 123 is formed of aluminium (Al) metal or Cu.
  • a coating solution that contains a composition of a liquid heat-decaying adhesive resin is applied onto the passivation film 122 and the outer lead wiring 123 on the surface of the semiconductor wafer 121 , in a mode of spin-coating. Then, this is baked at 80° C. or so to thereby form a heat-decaying adhesive resin layer 124 thereon.
  • the heat-decaying adhesive resin layer 124 is formed of a polyoxyalkylene resin having a thickness of 1 ⁇ m or so.
  • solder particles 125 having a size of 20 ⁇ or so are disposed at the position of the outer lead wiring 123 , and these are adhered to the surface of the heat-decaying adhesive resin layer 124 above the outer lead wiring 123 .
  • every solder particle 125 is sucked all at a time by every nozzle of a large number of vacuum suction nozzles, and all the solder particles 125 are positioned on the outer lead wiring 123 on the semiconductor chip, and these are adhered all at a time to the thus-positioned surface of the heat-decaying adhesive resin layer 124 . This operation is carried out for all the semiconductor chips on the semiconductor wafer 121 .
  • the solder bumps 126 are formed on the outer lead wiring 123 of the semiconductor wafer 121 .
  • the heat-decaying adhesive resin layer 124 on the outer lead wiring 123 is pyrolyzed and completely decayed simultaneously with the above-mentioned heat treatment.
  • the bumps of the type are formed mainly according to a plating process. In this Embodiment 3, the operability is significantly improved, therefore enabling high producibility.
  • solder bumps 126 can be formed in the simple process that comprises disposition of the solder particles 125 on the outer lead wiring 123 followed by heat treatment thereof.
  • the semiconductor wafer with the solder bumps 126 formed thereon is diced into semiconductor chips, and the semiconductor chips are bump-bonded to resin-encapsulated semiconductor devices or wiring boards according to a flip-chip-bonding process.
  • two different types of semiconductor chips may be bump-bonded according to a butt-joint bonding process, and accordingly, COC (chip-on-chip), a type of high-density MCPs (multi-chip packages) can be fabricated in a simplified manner and at high reliability. In that manner, electronic system integration according to the above-mentioned packaging technology is thereby promoted.
  • the conductive particles transfer sheet that comprises the heat-decaying material of the invention is not limited to the above-mentioned embodiments, but may be changed and modified in any desired manner within the technical idea of the heat-decaying material of the invention.
  • the conductive fine particles are spherical solder balls or spherical solder particles.
  • the conductive fine particles may also be columnar solder balls or columnar solder particles.
  • the conductive fine particles may be formed of any other low-melting-point alloys than solder. For example, metals of Au, Cu and Al are employable.
  • the heat-decaying adhesive resin is decayed by heating and thereafter the conductive fine particles are melt-bonded to the electrodes of electronic parts for electrical connection.
  • the conductive particles transfer sheet that comprises the heat-decaying material of the invention has conductive fine particles disposed on a heat-decaying adhesive resin layer or sheet.
  • the heat-decaying adhesive resin (sheet) is meant to indicate a single-layered sheet of a heat-decaying adhesive that decomposes into vapor when heated, or decomposes and vaporizes to lose its solid form, or a multi-layered sheet having an adhesive layer of such a heat-decaying adhesive.
  • the substrate may not decay so far as the heat-decaying adhesive layer may decay.
  • the entire sheet including the substrate may decay by heating.
  • heat-decaying adhesives are known, for example, polymethylenemalonic acid diesters, polybutylene, nitrocellulose, ⁇ -methylstyrene polymer, propylene carbonate polymer, polyalkyl (meth)acrylates, copolymers of carboxylic acid dihydrazides and diisocyanates, peroxides of these polymers, as well as tackified compositions of such polymers optionally containing a plasticizer such as dibutyl phthalate or dioctyl phthalate or a softener such as xylene oil, terpene oil or paraffin wax added thereto.
  • polybutene and polylauryl methacrylate may also be used as the heat-decaying adhesive.
  • the surface metal layer of the conductive fine particles or the conductive fine particles themselves are generally melted and bonded to them in the solder reflow step of the process. Therefore, when an adhesive capable of decaying at the reflow temperature falling between 150 and 260° C. is used, then the heat-decaying adhesive may be decayed in the reflow step, and the process may be significantly simplified. In addition, the heat-decaying adhesive can be used even in electronic parts relatively poorly resistant to heat.
  • the crosslinkable silyl group includes, for example, an oxime-silyl group, an alkenyloxysilyl group, an acetoxysilyl group, a halogenosilyl group, a vinylsilyl group, a silanol group.
  • alkoxysilyl-terminated polyoxyalkylene resin is favorable as it gives rubber-like crosslinked resin of good elasticity.
  • the alkoxysilyl group includes, for example, a methoxysilyl group, an ethoxysilyl group, a propyloxysilyl group, an isopropyloxysilyl group, a butoxysilyl group, a tert-butoxysilyl group, a phenoxysilyl group, a benzyloxysilyl group.
  • dialkoxysilyl groups or trialkoxysilyl groups the alkoxy groups may be the same or different alkoxy groups may be combined.
  • One or more such crosslinked silyl groups may be used herein either singly or as combined. Different types of polyoxyalkylene resins, or polyoxyalkylene resins having different types of crosslinkable silyl groups may also be combined for use herein.
  • the crosslinkable silyl group-having polyoxyalkylene resin preferably used is a photoreactive catalyst having a functional group of formula (2).
  • the crosslinkable silyl group-having polyoxyalkylene resin can be crosslinked and cured through exposure to light such as visible rays, UV rays or electron rays (this may be hereinafter referred to as light irradiation).
  • light irradiation a photoreactive catalyst having a functional group of formula (2).
  • carboxylic acid anhydrides, carboxylic acid imides and diacylphosphine oxides are preferred as their photoreactivity is high and as their solubility in crosslinkable silyl group-having polyoxyalkylene resins is also high.
  • One or more such photoreactive catalyst may be used herein either singly or as combined.
  • a sensitizer may be added to the crosslinkable silyl group-having polyoxyalkylene resin composition. Containing a sensitizer, the photoreactivity of the resin increases and therefore, the time for light irradiation to the resin composition may be shortened and the light irradiation energy thereto may be reduced, and the composition may be uniformly crosslinked and cured from its surface to its depth.
  • the sensitizer includes, for example, acetophenone derivative compounds such as 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ ′-dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone; benzoin ether compounds such as benzoin ethyl ether, benzoin propyl ether; ketal derivative compounds such as benzyldimethyl ketal; halogenoketones; acylphosphine oxides; acyl phosphonates; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone; bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,
  • the heat-decaying adhesive sheet of the invention is favorably used.
  • a transfer sheet for circuit formation that comprises the heat-decaying material of the invention is described below.
  • the transfer sheet for circuit formation that comprises the heat-decaying material of the invention is characterized in that it comprises an adhesive sheet of the heat-decaying material of the invention and a circuit pattern formed on the surface of the adhesive sheet.
  • FIG. 6( a ) shows a case of using an adhesive sheet of the heat-decaying material of the invention.
  • FIG. 6( b ) and FIG. 6( c ) each show a case of a composite adhesive sheet that partly contains the heat-decaying material of the invention.
  • FIG. 6( b ) is a case of an adhesive sheet having a laminate structure of a heat-decaying material and a non-heat-decaying resin;
  • FIG. 6( c ) is a case of an adhesive sheet formed by mixing different resin materials such as a heat-decaying material and a non-heat-decaying resin.
  • the non-heat-decaying resin means an ordinary resin not decomposing under heat.
  • the transfer sheet 21 for circuit formation comprises an adhesive sheet 22 formed of only a heat-decaying material having a thickness of from 10 ⁇ m to 500 ⁇ m, and a circuit pattern-forming metal layer 23 formed on the surface of the sheet 22 .
  • the transfer sheet 21 for circuit formation comprises an adhesive sheet 22 of a composite film formed of a resin substrate 22 a of a non-heat-decaying resin and a heat-decaying material layer 22 b , and a circuit pattern-forming metal layer 23 formed on the surface of the sheet 22 .
  • the adhesive sheet 22 has a laminate structure of the resin substrate 22 a and the heat-decaying resin layer 22 b , and the metal layer 23 is formed on the surface of the heat-decaying resin layer 22 b.
  • the composite film is not limited to the above-mentioned laminate structure.
  • the sheet 21 may comprise an adhesive sheet 22 c formed of a mixture of different types of resin material including a heat-decaying resin, and a circuit pattern-forming metal layer 23 is formed on the surface of the sheet 22 c .
  • the resin mixture for the adhesive sheet 22 c may be a mixture of a heat-decaying resin and a non-heat-decaying resin.
  • a heat-decaying resin composition and a non-heat-decaying resin composition may be mixed to form a mixture condition; or a heat-decaying resin and a non-heat-decaying resin may be mixed to form separated phases.
  • the phase separation is caused by the light irradiation or the heat treatment of the solution of a heat-decaying resin composition and a non-heat-decaying resin composition in a solvent, and, as a result, the adhesive sheet may have, for example, a large number of isolated small masses of the heat-decaying resin in the matrix (phase) of the non-heat-decaying resin.
  • the resulting adhesive sheet may also have the same structure as above.
  • the composite film may comprise a mixture of different types of heat-decaying resins that differ in point of the heat-decaying temperature.
  • the above-mentioned heat-decaying resin or the heat-decaying resin layer For rapidly decaying the above-mentioned heat-decaying resin or the heat-decaying resin layer, it must be heated generally at 250 to 400° C. However, when circuit boards are exposed to a high temperatures for a long period of time, then it may have some negative influences on the properties of the circuit boards. For it, in addition, a large-scale device is needed. On the other hand, when the layer peeling is attained by the pressure of the vapor to be generated through the decomposition of the heat-decaying resin as will be described hereinunder, it is desirable to use a heat-decaying resin capable of rapidly decaying at a possibly lower temperature. Further, as will be also described hereinunder, the acceptable heating temperature in production of electronic parts is often a relatively low temperature of 200° C. or lower.
  • the present inventors have assiduously studied various heat-decaying materials that have heretofore been known to be able to decay at relatively low temperatures and, as a result, have found that the heat-decaying resin of the invention is effective.
  • the resin prepared by crosslinking a crosslinkable silyl group-having polyoxyalkylene resin can rapidly decay when heated at 150 to 170° C., and, in addition, it has good adhesiveness to materials of a broad range such as metals and resins, and moreover, when it is shaped into sheets, the resulting sheets have a suitable sheet strength.
  • the adhesive sheet 22 comprises a mixture of a heat-decaying resin and a non-heat-decaying resin, for example, when it comprises a mixture with any of the above-mentioned heat-decaying resin, then the proportion of the heat-decaying resin to the heat-decaying resin-containing resin composition is not specifically defined, but is preferably at least 10% by weight.
  • the adhesive sheet When the heat-decaying resin is the principal component of the adhesive sheet 22 and when it accounts for a major part of the sheet, then the adhesive sheet may be substantially decayed by heating.
  • the vapor generated through decomposition of the heat-decaying resin may act to peel at least a part of the adhesive face of the adhesive sheet from the circuit pattern to thereby lower the adhesiveness therebetween, so far as the proportion of the heat-decaying resin is at least 10% by weight, and even in this case, therefore, the adhesive sheet could be readily peeled.
  • the heat-decaying resin-containing resin composition further contains a crosslinkable resin composition capable of crosslinking through energy stimulation applied thereto, for example, through exposure to light, electron rays or ion beams.
  • the adhesive sheet When some energy stimulation is applied to the adhesive sheet before the heat-decaying resin is decomposed to give a vapor and when the crosslinkable resin component is thereby crosslinked, then the adhesive sheet may be entirely cured and it may release more efficiently the vapor generated through the decomposition of the heat-decaying resin, and as a result, the adhesive sheet may be more readily peeled.
  • the proportion of the crosslinkable resin component to be in the heat-decaying resin-containing resin composition is not specifically defined, but is preferably at least 30% by weight of the composition. If the ratio of the crosslinkable resin component is less than 30% by weight, then the entire adhesive sheet could not be sufficiently cured.
  • the crosslinkable resin component that may crosslink through energy stimulation applied thereto is, for example, a photocurable adhesive that comprises a polymerizable polymer of an alkyl acrylate and/or an alkyl methacrylate having a radical-polymerizable unsaturated bond in the molecule, and a radical-polymerizable polyfunctional oligomer or monomer, as the principal ingredients thereof, and optionally contains a photopolymerization initiator; or a thermosetting adhesive that comprises a polymerizable polymer of an alkyl acrylate and/or an alkyl methacrylate having a radical-polymerizable unsaturated bond in the molecule, and a radical-polymerizable polyfunctional oligomer or monomer, as the principal ingredients thereof, and optionally contains a thermal polymerization initiator.
  • a photocurable adhesive that comprises a polymerizable polymer of an alkyl acrylate and/or an alkyl methacrylate having a radical-polymeriz
  • the post-curable adhesive such as the photocurable adhesive or thermosetting adhesive of the type may uniformly and rapidly polymerizes and cures as a whole of the adhesive through exposure to light or heat, thereby giving an integrated cured body. Accordingly, the elastic modulus of the polymerized and cured body of the adhesive extremely increases and the adhesive force thereof greatly lowers.
  • the heat-decaying resin is decomposed to generate a vapor in the hard cured body, then a major part of the generated vapor is let outside, and the thus-released vapor acts to peel at least a part of the adhesive face from the adhered object, thereby lowering the adhesiveness therebetween.
  • the polymerizable polymer may be obtained, for example, by previously preparing a (meth)acrylic polymer having a functional group in the molecule (hereinunder referred to as “functional group-containing (meth)acrylic polymer”), followed by reacting it with a compound having a functional group capable of reacting with the above-mentioned functional group, and a radical-polymerizable unsaturated bond in the molecule (hereinunder referred to as “functional group-having unsaturated compound”).
  • the functional group-containing (meth) acrylic polymer is a polymer that is adhesive at room temperature, and it may be obtained through ordinary copolymerization of a main monomer, alkyl acrylate and/or alkyl methacrylate in which the alkyl-group generally has from 2 to 18 carbon atoms, with a functional group-containing monomer and optionally with any other modifying monomer copolymerizable with them, like ordinary (meth)acrylic polymers.
  • the functional group-containing (meth)acrylic polymer may have a weight-average molecular weight of generally from 200,000 to 2,000,000 or so.
  • the functional group-containing monomer includes, for example, carboxyl group-having monomers such as acrylic acid, methacrylic acid; hydroxyl group-having monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate; epoxy group-having monomers such as glycidyl acrylate, glycidyl methacrylate; isocyanate group-having monomers such as isocyanatoethyl acrylate, isocyanatoethyl methacrylate; amino group-having monomers such as aminoethyl acrylate, aminoethyl methacrylate.
  • carboxyl group-having monomers such as acrylic acid, methacrylic acid
  • hydroxyl group-having monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate
  • epoxy group-having monomers such as glycidyl acrylate, glycidyl methacrylate
  • the other copolymerizable modifying monomer is, for example, various monomers used for ordinary (meth)acrylic polymers, such as vinyl acetate, acrylonitrile, styrene.
  • the functional group-containing unsaturated compound to be reacted with the functional group-containing (meth)acrylic polymer may be selected from those mentioned hereinabove for the functional group-containing monomers in accordance with the functional group of the functional group-containing (meth) acrylic polymer.
  • the functional group of the functional group-containing (meth)acrylic polymer is a carboxyl group
  • epoxy group-having monomers and isocyanate group-having monomers may be used for it
  • the functional group is a hydroxyl group
  • isocyanate group-having monomers may be used
  • the functional group is an epoxy group
  • carboxyl group-having monomers and amido group-having monomers such as acrylamide may be used
  • the functional group is an amino group, then epoxy group-having monomers may be used.
  • the polyfunctional oligomer or monomer preferably has a molecular weight of at most 10,000. More preferably, it has a molecular weight of at most 5,000 and has from 2 to 20 radical-polymerizable unsaturated bonds in the molecule, for more efficient three-dimensional network formation through heating or exposure to light.
  • polyfunctional oligomer or monomer are, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, and methacrylates corresponding to these.
  • these polyfunctional oligomers and monomers may be used herein either singly or as combined.
  • the photopolymerization initiator is, for example, one capable of being activated when exposed to light having a wavelength of from 250 to 800 nm.
  • the photopolymerization initiator of the type includes, for example, acetophenone derivative compounds such as methoxyacetophenone; benzoin ether compounds such as benzoin isopropyl ether, benzoin isobutyl ether; ketal derivative compounds such as benzyldimethyl ketal, acetophenonediethyl ketal; phosphine oxide derivative compounds; and photoradical polymerization initiators such as bis( ⁇ 5-cyclopentadienyl)titanocene derivative compounds, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimehtylthioxanthone, diethylthioxanthone, ⁇ -hydroxycyclohexylphenyl ketone, 2-hydroxymethylphen
  • the thermal polymerization initiator is one that decomposes under heat and generates an active radical for initiating polymerization and curing.
  • it includes dicumylperoxide, di-t-butylperoxide, t-butylperoxybenzoate, t-butylhydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, di-t-butyl peroxide.
  • cumeme hydroperoxide, paramenthane hydroperoxide and di-t-butyl peroxide are preferred.
  • thermal polymerization initiators are commercially available, and are usable herein with no specific limitation. For example, preferred are Perbutyl D, Perbutyl H, Perbutyl P, Permenta H (all by Nippon Yushi). One or more of these thermal polymerization initiators may be used herein either singly or as combined.
  • the circuit pattern to be formed on the surface of the adhesive sheet is formed of, for example, metal foil or conductive paste layer.
  • the metal foil may be foil of metal suitable for circuit pattern formation and is, for example, foil of high-melting-point metal such as tungsten, molybdenum; low-resistance metal such as gold, silver, copper, aluminium; or alloy containing at least one such low-resistance metal.
  • the lowermost limit of the thickness of the metal foil is 1 ⁇ m, and the uppermost limit thereof is 100 ⁇ m. If smaller than 1 ⁇ m, then the resistivity of the circuit pattern to be formed of the metal foil may be high and the circuit boards produced may be unsuitable. If larger than 100 ⁇ m, then an insulating substrate or a ceramic-green sheet may deform greatly when the metal foil is laminated thereon in producing circuit boards that will be mentioned hereinunder, and, in addition, when the circuit pattern formed of the metal foil is transferred onto an insulating substrate or a ceramic green sheet, the buried amount of the circuit pattern may increase and the degree of deformation of the insulating substrate or the ceramic green sheet may increase.
  • the insulating substrate or the ceramic green sheet may be readily deformed when the resin is cured.
  • the etching may be difficult, and this may cause another problem in that a micropatterned circuit is difficult to form with accuracy.
  • the lowermost limit of the thickness is 5 ⁇ m, and the uppermost limit thereof is 50 ⁇ m.
  • the surface of the metal foil that is to be on the side of the adhesive sheet may be roughened to have fine irregularities in order to increase the adhesiveness thereof to the adhesive sheet.
  • the surface of the metal foil may be roughened to have fine irregularities of from 0.2 to 0.7 ⁇ m or so in terms of the surface roughness Ra defined by JIS B0601.
  • the other surface of the metal foil opposite to the adhesive sheet side may also be roughened in the same manner to have fine irregularities, whereby the bonding force between the insulating substrate or ceramic green sheet and the circuit pattern may be increased.
  • the conductive paste layer is, for example, a layer of a resin paste prepared by adding conductive fine particles, such as noble metal particles of gold, silver or copper, or solder particles or metal-plated resin particles, to a binder resin, or a layer of a metal paste of cream solder or the like.
  • the circuit pattern-having metal layer 23 is formed according to a patterning screen-printing method of processing the metal foil adhered to the adhesive sheet 22 , or according to a plating method.
  • the method of forming a circuit pattern by patterning the metal foil is not specifically defined, and for example, a known resist method is employed for it.
  • the resist method comprises applying a photoresist onto the entire surface of the metal foil, exposing it to light via a mask of a predetermined pattern, developing it, and then etching it in a mode of plasma etching or chemical etching to thereby remove the metal foil in the non-pattern region (the region from which the photoresist is removed). Accordingly, the intended circuit pattern of the metal foil is formed.
  • Another method is also employable, which comprises applying a photoresist to the surface of metal foil in a predetermined circuit pattern form according to a screen printing process or the like, then exposing it to light in the same manner as above and thereafter etching it to form the intended circuit pattern. After the etching, some resist may remain on the circuit pattern, but it may be removed with a resist remover, and the resulting circuit pattern is thereby cleaned. Accordingly, a transfer sheet for circuit formation is thus obtained, which has a circuit pattern formed on the surface of an adhesive sheet.
  • a method of baking the conductive paste layer and then processing it in the same manner as in the above-mentioned case of processing metal foil is also employable, which comprises screen-printing a conductive paste on a substrate, baking it to form a circuit pattern, and attaching the above-mentioned adhesive sheet to it to thereby form a circuit pattern of the conductive paste layer on the adhesive sheet.
  • Still another method may be employed, which comprises forming grooves corresponding to the circuit pattern on the surface of the adhesive sheet, and filling the grooves with a conductive paste by the use of a squeeze to thereby form a circuit pattern of the conductive paste on the adhesive sheet.
  • the transfer sheet for circuit formation that comprises the heat-decaying material of the invention has an adhesive sheet that comprises a heat-decaying resin capable of decomposing under heat or comprises a composite film containing such a heat-decaying resin, and therefore, when this is used for circuit transfer, the adhesive sheet decays, or its adhesive force lowers owing to the vapor generated through decomposition of the heat-decaying resin that constitutes the adhesive sheet and, as a result, the intended circuit pattern can be well transferred onto an insulating resin or a ceramic green sheet with no pattern disturbance even when the adhesive sheet has a high adhesive force. In addition, even when a circuit pattern having an extremely narrow line width is transferred, it can be well transferred with high accuracy.
  • the transfer sheet for circuit formation may optionally have metal foil or conductive paste layer formed on the surface of the adhesive sheet thereof.
  • the metal foil or the conductive paste layer is not patterned into a form of circuit pattern.
  • FIG. 7 includes cross-sectional views of a process scheme of using the transfer sheet for circuit formation of FIG. 6( a ); and FIG. 8 includes cross-sectional views of a process scheme of using the transfer sheet for circuit formation of FIG. 6( b ).
  • a transfer sheet 21 that comprises an adhesive sheet 22 and a circuit pattern-forming metal layer 23 on the surface thereof is prepared in the manner as above, and this is positioned to an insulating substrate 24 which is in a semi-cured condition, and then the two are bonded to each other.
  • the insulating substrate 24 is a substrate having insulating properties as will be described hereinunder.
  • a pressure of 100 kg/cm 2 or so is applied to the two, whereby a part or all of the metal layer 23 is embedded and fixed in the insulating substrate 24 .
  • the method of pressure-bonding the transfer sheet 1 for circuit formation and the insulating substrate 24 is not specifically defined.
  • herein employable is a method of bonding the two owing to the anchor effect by pressing; and a method of applying an adhesive to the insulating substrate and/or the circuit pattern of the transfer sheet for circuit formation, followed by bonding the two.
  • a method of thermally pressing the two at a suitable temperature is preferred. This is because, according to the method, a part or all of the thermosetting resin may be cured to have an increased adhesive force, and it evades troubles of circuit pattern mispositioning or transfer failure.
  • a single-layered circuit board is formed, which has the circuit pattern-having metal layer 23 transferred onto the insulating substrate 24 . Further, if desired, the insulating substrate 24 may be completely cured at a temperature falling between 250 and 300° C. A multi-layered circuit board may be formed by laminating these single-layered circuit boards.
  • a transfer sheet 21 for circuit formation is prepared in the manner as above, which comprises a laminate-structured adhesive sheet 22 of a composite film comprising a resin substrate 22 a and a heat-decaying resin layer 22 b , and a metal layer 23 formed on the surface of the heat-decaying resin layer 22 b .
  • the transfer sheet 21 is positioned to an insulating substrate 24 which is in a semi-cured condition, and then the two are bonded to each other under heat and pressure. In that manner, a part or all of the metal layer 23 is embedded and fixed in the insulating substrate 24 .
  • this is subjected to heat treatment at a temperature around 250° C. or so in a nitrogen atmosphere.
  • the heat-decaying resin layer 22 b to form the adhesive sheet 22 pyrolyzes and decays.
  • the resin substrate 22 a is lifted off though the pyrolysis of the heat-decaying resin layer 22 b , and this is completely separated from the metal layer 23 .
  • the insulating substrate 24 completely cures at the same time.
  • a single-layered circuit board is formed, which has the circuit pattern-having metal layer 23 transferred onto the insulating substrate 24 .
  • the adhesive sheet 22 greatly shrinks and completely peels from the metal layer 23 since the heat-decaying resin in the adhesive sheet 22 pyrolyzes and decays through the heat treatment at about 250° C.
  • the adhesive force of the adhesive sheet 22 c greatly lowers owing to the vapor generated through the decomposition of the heat-decaying resin, and the sheet 22 c peels from the metal layer 23 .
  • the circuit pattern-having metal layer 23 is transferred onto the insulating substrate 24 , and a single-layered circuit board is readily formed.
  • the insulating substrate 24 is formed of an ordinary thermosetting resin or a ceramic green sheet.
  • thermosetting resin is not specifically defined, including, for example, polyphenylene ether (PPE); bismaleimide resins such as bismaleimido-triazine (BT); and epoxy resins, polyimide resins, fluororesins, phenol resins.
  • PPE polyphenylene ether
  • BT bismaleimido-triazine
  • epoxy resins epoxy resins
  • polyimide resins fluororesins
  • phenol resins phenol resins
  • the thermosetting resin is liquid at room temperature.
  • the semi-cured thermosetting resin may contain a filler generally for increasing its strength.
  • the filler may be, for example, organic or inorganic power or fibers.
  • the inorganic filler is not also specifically defined, including, for example, SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , AlN, SiC, BaTiO 3 , SrTiO 3 , zeolite, CaTiO 3 , aluminium borate.
  • the inorganic filler is a powder of nearly spherical particles.
  • the mean particle size of the particles is at most 20 ⁇ m more preferably at most 10 ⁇ m, even more preferably at most 7 ⁇ m.
  • the inorganic filler may be fibrous, and may have a mean aspect ratio of at least 5.
  • the fibrous filler includes, for example, fibers of glass, and it may be in any form of woven fabric or nonwoven fabric, and may have any unlimited properties.
  • the organic filler includes, for example, aramid fibers, cellulose fibers.
  • thermosetting resin and the filler are used herein either singly or as combined.
  • the thermosetting resin and the filler are used in a ratio by volume of thermosetting resin/filler falling between 15/85 and 65/35.
  • thermosetting resin or a slurry containing a thermosetting resin and an inorganic filler is shaped into a sheet according to a doctor blade method or the like, and then it is heated to be in a semi-cured condition.
  • via-holes are formed in the insulating substrate by the use of a carbon dioxide gas laser or the like, and the via-holes are filled with a low-resistance metal powder of gold, silver, copper, aluminium or the like to form a via-hole conductor.
  • the transfer sheet In the step of pressure-bonding the circuit pattern-having face of the transfer sheet for circuit formation mentioned above to an insulating substrate or the like followed by attaching or embedding the circuit pattern into the insulating substrate, when a via-hole conductor is formed in the insulating substrate, then the transfer sheet is so positioned to the insulating substrate that the circuit pattern could overlap with the surface-exposed part of the via-hole conductor.
  • the ceramic green sheet may be produced, for example, by shaping a mixture of a ceramic powder of alumina or the like, a binder resin and a plasticizer, into a sheet.
  • the ceramic green sheet When the insulating substrate 24 is formed of a ceramic green sheet, the ceramic green sheet must be baked at a high temperature (from 600 to 1500° C. or so) after the circuit pattern-having metal layer 23 has been transferred onto the insulating substrate 24 . Accordingly, especially in this case, the metal layer 23 is formed of a high-melting-point metal such as tungsten or molybdenum mentioned above.
  • a first method of producing circuit boards comprises using the transfer sheet for circuit formation mentioned above.
  • the method includes a step of pressure-bonding an insulating substrate or a ceramic green sheet onto the circuit pattern of the above-mentioned transfer sheet for circuit formation and attaching or embedding the circuit pattern into the insulating substrate of the ceramic green sheet, and a step of decomposing the heat-decaying resin by heating thereby to decay or deform the adhesive sheet and to transfer the circuit pattern onto the insulating substrate or the ceramic green sheet.
  • the adhesive sheet when the adhesive sheet is formed of a heat-decaying resin or the adhesive sheet is formed of a resin composition comprising the heat-decaying resin as the principal ingredient thereof, then the adhesive sheet is substantially decayed by heating. Accordingly, the process does not require a step of peeling the adhesive sheet from the circuit pattern, and its production efficiency (producibility) and workability may be thereby improved.
  • the adhesive force of the adhesive sheet is reduced by the vapor generated through decomposition of the heat-decaying resin, and therefore the adhesive sheet could be readily peeled from the circuit pattern.
  • the adhesive sheet contains a crosslinkable resin component capable of crosslinking through energy stimulation applied thereto, then it is desirable that some energy stimulation is applied to the sheet so as to crosslink the crosslinkable resin component before the sheet is heated to decompose the heat-decaying resin therein.
  • the adhesive force of the adhesive sheet could be greatly lowered, and the adhesive sheet could be more readily peeled from the circuit pattern.
  • the heat-decaying resin polymerizes owing to the crosslinkable resin component capable of crosslinking through exposure to light, and it readily undergoes phase separation in the matrix (phase) mentioned above.
  • the heat-decaying resin when a crosslinked resin of the above-mentioned crosslinkable silyl group-having polyoxyalkylene resin is used for the heat-decaying resin, then the heat-decaying resin may be decomposed by heating at 150 to 170° C.
  • the crosslinked resin of the above-mentioned crosslinkable silyl group-having polyoxyalkylene resin can be rapidly decomposed in an oxygen atmosphere even at a relatively low temperature. Accordingly, the decomposition time for the heat-decaying resin can be controlled by controlling the oxygen concentration in the heating atmosphere gas.
  • a second method of producing circuit boards comprises using the transfer sheet for circuit formation mentioned above.
  • the method includes a step of forming a circuit pattern by patterning the metal foil or the conductive paste layer of the transfer sheet for circuit formation, a step of pressure-bonding an insulating substrate or a ceramic green sheet onto the circuit pattern and attaching or embedding the circuit pattern into the insulating substrate of the ceramic green sheet, and a step of decomposing the heat-decaying resin by heating thereby to decay or deform the adhesive sheet and to transfer the circuit pattern onto the insulating substrate or the ceramic green sheet.
  • the production method includes the step of forming a circuit pattern by patterning the metal foil or the conductive paste layer of the transfer sheet for circuit formation.
  • circuit pattern formed of a conductive paste layer is kept pressure-bonded to the insulating substrate or the ceramic green sheet, they may be heated so as to decay or deform the adhesive sheet and to transfer the circuit pattern formed of a conductive paste layer onto the insulating substrate or the ceramic green sheet.
  • the step of pressure-bonding the insulating substrate or the like onto the circuit pattern and attaching or embedding the circuit pattern into the insulating substrate, and the step of decomposing the heat-decaying resin by heating thereby to transfer the circuit pattern onto the insulating substrate or the ceramic green sheet may be the same as those in the above-mentioned first method for producing circuit boards.
  • a transfer sheet for circuit formation that contains the above-mentioned heat-decaying resin is used, and therefore, even when the adhesive sheet has a high adhesive force, the circuit pattern can be well transferred onto the insulating resin or the like with no pattern disturbance. In addition, even when a circuit pattern having an extremely narrow line width is transferred at high density, it can be well transferred with high accuracy.
  • the method does not require any additional step of reducing the adhesive force of the adhesive sheet, but requires only the step of heating the adhesive sheet to decay or peel the adhesive sheet. Therefore, the production efficiency (producibility) and the workability of the method may be significantly improved.
  • the heat-decaying material of the invention is effective for pattern formation.
  • FIG. 11 includes cross-sectional views of a process scheme that comprises patterning of an etching mask by the use of the heat-decaying resin film mentioned above, and patterning an insulator film via the mask for pattern formation.
  • a decaying resin coating solution prepared by dissolving a crosslinkable silyl group-having polyoxypropylene resin and a diacylphosphine oxide compound in a solvent.
  • an insulator film 32 of silicon oxide is deposited on a semiconductor substrate 31 with various semiconductor elements (not shown) formed thereon, and the above-mentioned decaying resin coating solution is applied onto the insulator film 32 in a mode of spin coating. Then, after the spin coating, this is pre-baked at a temperature not higher than 100° C. to vaporize the unnecessary solvent. In that manner, a heat-decaying resin film 33 having a thickness of 1 ⁇ m or so is formed. In this, the coating operation may be effected under irradiation with ordinary fluorescent light. As opposed to this, the coating step in conventional photolithography requires a special working room capable of completely blocking UV light.
  • the laser beams 34 are heat beams, and give heat energy to the heat-decaying resin film 33 whereby the irradiated region of the film is heated up to 200° C. to 250° C. or so.
  • the heat energy applied thereto the irradiated region of the heat-decaying resin film 33 is pyrolyzed and decayed. In that manner, the heat-decaying resin film 33 is patterned to form an etching mask 35 .
  • the functional group in the resist is sensitive to the light in the direct-patterning process, and the base resin of the resist is therefore changed through exposure to light. Specifically, the copolymerization of the base resin is cleaved (in positive resists) or the polymerization is promoted (in negative resists). In that manner, the base resin having changed through exposure to light is dissolved in the next developing step to attain pattern formation.
  • the first embodiment of the method of pattern formation by the use of the heat-decaying material of the invention does not require the development step as in conventional photolithography, and therefore enables significant cost reduction in pattern formation.
  • the light source usable for the light irradiation may be any one that covers a wavelength range in which the polyoxyalkylene resin composition is sensitive to the light and begins to cure.
  • the light source usable for the light irradiation includes low-pressure mercury lamp, middle-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, excimer laser, chemical lamp, black light lamp, microwave-excited mercury lamp, metal halide lamp, sodium lamp, halogen lamp, xenon lamp, fluorescent lamp, sunlight, electron beam radiator.
  • the etching mask 35 a thus formed from the etching mask through exposure to light may have improved dry-etching resistance that will be mentioned below, and may well function as a dry-etching mask.
  • the insulator film 32 is dry-etched with plasma, via the etching mask 35 a .
  • an opening 37 is formed in the insulator film 32 .
  • the removal of the etching mask 35 a in the first embodiment of the method of pattern formation may be attained in a simple oven, as compared with the ashing removal in plasma in the prior art, and, in addition, the removal method is extremely simple. Accordingly, since the removal of the etching mask after used is extremely simple, and the cost of pattern formation can be greatly reduced.
  • the heating when the heating is effected under reduced pressure, then the removal may be effected more efficiently.
  • electron beams may be used in place of the laser beams for the thermal energy impartation.
  • the laser source further usable herein are UV laser light source, and excimer laser light source.
  • the heat-decaying resin to be used for the above-mentioned pattern formation includes, for example, polymethylenemalonic acid diesters, polybutylene, nitrocellulose, ⁇ -methylstyrene polymer, propylene carbonate polymer, polyalkyl (meth)acrylates, copolymers of carboxylic acid dihydrazides and diisocyanates, peroxides of these polymers, as well as tackified compositions of such polymers optionally containing a plasticizer such as dibutyl phthalate or dioctyl phthalate or a softener such as xylene oil, terpene oil or paraffin wax added thereto.
  • polybutene and polylauryl methacrylate may also be used as the heat-decaying resin.
  • the heat-decaying material as defined in the invention. Further, among them, we the present inventors have found that the heat-decaying resin film prepared by crosslinking a crosslinkable silyl group-having polyoxyalkylene resin composition can be rapidly decayed when heated at 150 to 260° C.
  • the heat-decaying resin prepared by crosslinking a crosslinkable silyl group-having polyoxyalkylene resin composition may be the same as those described in detail in the section of the conductive particles transfer sheet.
  • FIG. 12 includes cross-sectional views of a process scheme that comprises patterning of a lift-off mask by the use of the heat-decaying resin film mentioned above, and patterning of a conductor film for wiring by the use of it.
  • the same elements as those in the first embodiment are indicated by the same reference numerals.
  • a decaying resin coating solution prepared by dissolving the above-mentioned, crosslinkable silyl group-having polyoxypropylene resin and a diacylphosphine oxide compound in a solvent.
  • a silicon oxide insulator film 32 is deposited on a semiconductor substrate 31 , and the above-mentioned decaying resin coating solution is applied onto the insulator film 32 in a mode of spin coating. Then, after the spin coating, this is pre-baked at a temperature of 80° C. or so to vaporize the unnecessary solvent. In that manner, a heat-decaying resin film 33 having a thickness of 1.5 ⁇ m or so is formed.
  • FIG. 12( b ) this is exposed to heat beams or laser beams 34 according to a direct-patterning process.
  • YAG laser is used for the light source.
  • Heat energy is thus imparted to the heat-decaying resin film 33 and the irradiated region of the film is thereby heated at 200° C. or so.
  • heat may concentrate and remain in the surface of the insulator film 32 formed of silicon oxide of poor thermal conductivity, and therefore the heat-decaying resin film 33 nearer to the insulator film 32 is more readily pyrolyzed.
  • a lift-off mask 39 having a lift-off opening 38 is formed as in FIG. 12( b ), in which the opening 38 has a reverse-tapered cross-sectional profile.
  • the formation of the lift-off mask 39 having the lift-off opening 38 does not require at all the development step as in conventional photolithography, like in the first embodiment. Accordingly, the pattern formation in this embodiment enables significant cost reduction, as so mentioned hereinabove.
  • a conductor film 310 of tungsten (W) or the like, for example, having a thickness of 0.5 ⁇ m or so is formed on the lift-off mask 39 a in a mode of sputtering film formation.
  • W tungsten
  • a collimate-sputtering process excellent in rectilinear deposition is preferred.
  • a wiring 311 may be formed on the insulator film 32 on the semiconductor substrate 31 , as in FIG. 12( e ).
  • the life-off mask is formed of a resist film, and in the lift-off step, the lift-off mask formed of a resist film is dissolved in a chemical of an organic solvent and removed. Through the dissolution and removal of the lift-off mask, the conductor film deposited on the lift-off mask is lifted off and removed, and wiring is thereby formed.
  • the chemical as in the conventional lift-off step is not used, and therefore, the lift-off operation is safe and its operability is improved. In addition, the pattern formation cost is thereby reduced.
  • the quantity of light of YAG laser is varied, then the reversed taper could not be formed but the lift-off operation is still possible.
  • FIG. 13 and FIG. 14 each include cross-sectional views of a process scheme that comprises patterning of an etching mask by the use of the heat-decaying resin film mentioned above, and patterning of a semiconductor film by the use of it.
  • the same elements as those in the first embodiment are indicated by the same reference numerals.
  • a decaying resin coating solution prepared by dissolving the above-mentioned, crosslinkable silyl group-having polyoxypropylene resin and a diacylphosphine oxide compound in a solvent, like in the first and second embodiments.
  • a thermal oxide film (not shown) is formed on the surface of a semiconductor substrate 31 , and a semiconductor thin film 312 of a polycrystalline silicon film or the like is deposited on the thermal oxide film, and the above-mentioned decaying resin coating solution is applied onto the semiconductor thin film 312 in a mode of spin coating. Then, after the spin coating, this is pre-baked at a temperature of 80° C. or so to vaporize the unnecessary solvent. In that manner, a heat-decaying resin film 33 having a thickness of 1 ⁇ m or so is formed.
  • this is exposed to light in the same manner as in conventional photolithography.
  • a reticle 315 that comprises a quartz glass substrate 313 and a light-shielding film pattern 314 formed on its surface, as a photomask
  • light for exposure 316 is applied to this in a mode of ordinary reduced projection exposure and the heat-decaying resin film 33 is thereby patterned through exposure transfer.
  • a photocured region 33 a is formed in a predetermined area of the heat-decaying resin film 33 .
  • ArF excimer layer (wavelength: about 193 nm) is used for the light for exposure 316 .
  • this is subjected to heat treatment at a temperature of 150° C. or so.
  • the heat-decaying resin in the region except the photocurable region 33 a of the heat-decaying resin 33 is pyrolyzed and completely decayed.
  • the photocurable region 33 a of the heat-decaying resin film 33 does not pyrolyze at the above-mentioned temperature of 150° C. or so, but remains to exist as it is.
  • the heat-decaying resin film 33 is patterned to form an etching mask 317 on the semiconductor film 312 .
  • the above-mentioned temperature for heat treatment is so designed as to be higher than the temperature at which the heat-decaying resin film 33 in the region not irradiated with the light 316 decomposes and decays, but lower than the temperature at which the heat-decaying resin film 33 in the region irradiated with the light 316 , or that is, the photocurable region 33 a thereof decomposes and decays.
  • the functional group in the resist is sensitive to light, and the base resin of the resist is therefore changed through exposure to light in the step of FIG. 16( b ) as so mentioned hereinabove.
  • the copolymerization of the base resin is cleaved (in positive resists) or the polymerization is promoted (in negative resists). In that manner, the base resin having changed through exposure to light is dissolved in the next developing step to attain pattern formation.
  • this embodiment also does not require a development step as in conventional photolithography, and enables significant cost reduction in pattern formation.
  • the semiconductor thin film 312 is dry-etched with plasma, via the etching mask 317 .
  • a gate electrode 318 is formed.
  • this is subjected to heat treatment at a temperature falling between 200° C. and 250° C. or so.
  • the etching mask 317 formed of the heat-decaying resin is pyrolyzed and is completely decayed and removed.
  • the atmosphere for the heat treatment may be dry air.
  • the gate electrode 318 is formed on the semiconductor substrate 31 through patterning of the semiconductor thin film 312 .
  • the removal of the etching mask 317 is extremely simple as compared with the ashing removal in plasma in the prior art, and this enables significant cost reduction in patterning.
  • a polypropylene glycol diacrylate-based photocurable resin may be added to the decaying resin coating solution for use herein. Accordingly, such a photo crosslinkable material is added to it, and the decay temperature T 1 in the exposed region can be selectively elevated over the decay temperature T 0 in the non-exposed region. With that, when the coating layer is heated at a temperature T (T 0 ⁇ T ⁇ T 1 ), then the resist pattern can be more readily formed.
  • this is heated at T (T>T 1 ), and the resist pattern can be removed.
  • FIG. 15 includes cross-sectional views of a process scheme that comprises patterning of a plating mask by the use of the heat-decaying resin film mentioned above, and patterning of a metal film for bumps by the use of it.
  • the same elements as those in the first embodiment are indicated by the same reference numerals.
  • a decaying resin coating solution prepared by dissolving the above-mentioned, crosslinkable silyl group-having polyoxypropylene resin and a diacylphosphine oxide compound in a solvent.
  • an insulator film 32 of silicon oxide is deposited on a semiconductor substrate with various semiconductor elements (not shown) formed thereon, and a thin Cu layer is formed on the insulator film 32 to be a feeder layer 319 , according to a sputtering process.
  • the above-mentioned, decaying resin coating solution is applied over this according to a spin-coating process, and a plating mask 321 having a plating opening 320 is formed in the same manner as that for the step of FIG. 11( b ).
  • the plating mask 321 is entirely exposed to light, whereby the composition that constitutes the heat-decaying resin film to form the pattern of the plating mask 321 is crosslinked and photocured.
  • this is plated in a plating bath filled with a plating solution that contains a divalent copper ion, for example, an aqueous solution of cupper sulfate having a copper ion content of from 5 to 200 g/liter or so.
  • a copper electrode 322 is formed to fill the plating opening 320 , as in FIG. 15( b ).
  • the photocured plating mask 321 does not swell in the plating bath and its pattern does not change.
  • this is subjected to heat treatment in a nitrogen atmosphere at a temperature falling between 200 and 250° C., as in FIG. 15( c ).
  • the plating mask 321 formed of the heat-decaying resin is pyrolyzed and completely decayed and removed.
  • the atmosphere for heat treatment may be dry air.
  • the metal film is patterned to give the copper electrode 322 formed on the insulator film 32 on the semiconductor substrate 31 .
  • the thin feeder layer 319 is removed by dry etching or ion milling in the subsequent step.
  • the plating mask 321 formed of the heat-decaying resin may be applied entirely in the same manner as above also to gold (Au) plating except copper plating. Patterning the metal film in the manner as above enables formation of bumps or wirings on semiconductor chips.
  • the pattern formation by the use of the heat-decaying material of the invention is not limited to the above-mentioned embodiments, and the embodiments may be suitably changed and modified within the technical scope of the invention.
  • the above-mentioned embodiments are to demonstrate production of semiconductor devices. Not limited to these, the invention is applicable to production of display devices such as liquid-crystal display panels, plasma display panels.
  • the etching treatment is for dry etching. Also not limited to it, the invention is applicable to wet etching.
  • the thus-prepared, heat-decaying material (paste) was applied onto a polyethylene terephthalate film and onto an aluminium plate having a thickness of 25 ⁇ m, so that its thickness could be 100 ⁇ m.
  • the coated object was exposed to UV ray at 365 nm from a high-pressure mercury lamp at a controlled irradiation intensity of 10 mW/cm 2 for 60 seconds. After thus exposed to UV ray, this was cured at 80° C. for 30 minutes to obtain a heat-decaying sheet.
  • the thus-prepared, heat-decaying material (paste) was applied onto a polyethylene terephthalate film and onto an aluminium plate having a thickness of 25 ⁇ m, so that its thickness could be 100 ⁇ m.
  • the coated object was exposed to UV ray at 365 nm from a high-pressure mercury lamp at a controlled irradiation intensity of 10 mW/cm 2 for 60 seconds. After thus exposed to UV ray, this was cured at 50° C. for 30 minutes to obtain a heat-decaying sheet.
  • the thus-prepared photocurable composition was applied onto a lubricant-processed polyethylene terephthalate film and onto an aluminium plate having a thickness of 25 ⁇ m, so that its thickness could be 100 ⁇ m.
  • the coated object was exposed to UV ray at 365 nm from a high-pressure mercury lamp at a controlled irradiation intensity of 2 mW/cm 2 for 30 minutes, and an adhesive sheet was thus obtained.
  • the heat-decaying sheets formed in Examples 1 and 2 and Comparative Example 1 were evaluated in point of cobwebbing from sheet, tacky feel, and decay time when heated at 150° C. and 250° C.
  • a thin and long polyethylene terephthalate sheet having a width of 25 mm and a thickness of 50 ⁇ m is attached to the adhesive layer of the adhesive sheet, and the sheet is peeled from its end. In this case, the sheet is visually observed as to whether or not cobwebbing is seen in the peeling interface.
  • the adhesive layer of the heat-decaying sheet is touched with fingers, and the sample is organoleptically evaluated as to whether it is sticky or not.
  • the adhesive sheet with an aluminium plate as its substrate is cut into a piece of 5 mm ⁇ 5 mm, and the resulting sample is put on a hot plate heated at a predetermined temperature.
  • the adhesive layer is visually observed, and its decay time is determined. After the decay of the layer, the weight of the residue remaining on the aluminium plate is measured, and the weight reduction by heating is calculated.
  • Example 2 In the same manner as in Example 1, the resulting crosslinked film was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • Example 2 In the same manner as in Example 1, the resulting crosslinked film was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 2 g of cumene hydroxyperoxide (peroxide as a decomposition promoter) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 2 g of AIBN (azo compound as a decomposition promoter) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • AIBN azo compound as a decomposition promoter
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 4 g of tin oxide (decomposition promoter) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 3 g of dodecylmercaptan (mercapto compound as a decomposition retardant) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 2 g of 1,6-hexamethylenediamine (amine compound as a decomposition retardant) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 2 g of dibutyltin dilaurate (organic tin as a decomposition retardant) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • a heat-decaying material (paste) was prepared in the same manner as in Example 1, to which, however, 3 g of tributyl borate (organic boron as a decomposition retardant) was added. This was formed into a heat-decaying sheet in the same manner as in Example 1.
  • Example 2 In the same manner as in Example 1, the resulting heat-decaying sheet was heated at 150° C., 250° C. and 300° C., and the decaying time and the weight of the residue after decay of the sample were determined. The results are shown below.
  • the heat-decaying sheet of Example 1 was heated in a nitrogen or oxygen concentration atmosphere as in the following Tables, at 250° C. or 300° C. for 5 minutes.
  • the weight reduction of the sheet after heated, the amount of the residue thereof, and the visual appearance thereof are shown in the Tables.
  • the oxygen concentration was measured with an oxygen concentration monitor alarm, Gastec's OXYTEC mini-monitor, GOA-6H-S, and indicated by percentage.
  • the oxygen concentration is a value obtained by subtracting the value of the above-mentioned oxygen concentration from 100.
  • the weight reduction and the amount of residue, the oxygen concentration in the Tables is a value obtained by subtracting the value of the above-mentioned oxygen concentration from 100.
  • tetraethoxysilane by Shin-etsu Chemical
  • 20 g of a hydrolyzing silyl group-containing polypropylene glycol (Asahi Glass' Exsester ESS-3630)
  • 3 g of a diacylphosphine oxide derivative (Ciba Specialty Chemical's Irgacure 819) were heated at about 40° C. in the dark and dissolved to be uniform.
  • the resulting composition was cast into a frame, width 10 mm ⁇ length 30 mm ⁇ depth 0.05 mm, formed of a steel sheet with an adhesive tape, and exposed to a high-pressure mercury lamp (365 nm, intensity 10 mW/cm 2 ⁇ 60 seconds) whereby the hydrolyzing silyl group-containing polypropylene glycol was crosslinked, and the size of the copolymer to be a heat-decaying material was controlled. After thus exposed to light, this was then cured at 20° C. for 48 hours at it was. A flexible film was obtained. The resulting film was cured in an oven at 250° C. for 10 minutes. A rigid porous plate having a residual organic content of at most 3% was obtained. The resulting rigid film was further cured at 400° C. for 30 minutes. The residual organic content was evaluated in terms of the loss weight of the object determined through thermal weight reduction (TGA, heating rate 10° C./min, highest temperature limit 600° C.)
  • tetraethoxysilane by Shin-etsu Chemical
  • 12 g of a hydrolyzing silyl group-containing polypropylene glycol (Asahi Glass' Exsester ESS-3630)
  • 8 g of ⁇ , ⁇ -diacryloyloxypolypropylene glycol (Toa Gosei's Aronix M-270)
  • 3 g of a diacylphosphine oxide derivative (Ciba Specialty Chemical's Irgacure 819) were heated at about 40° C. in the dark and dissolved to be uniform.
  • the resulting composition was cast into a frame, width 10 mm ⁇ length 30 mm ⁇ depth 0.05 mm, formed of a steel sheet with an adhesive tape, and exposed to a high-pressure mercury lamp (365 nm, intensity 10 mW/cm 2 ⁇ 60 seconds). After thus exposed to light, this was then cured at 20° C. for 24 hours at it was. A flexible film was obtained. The resulting film was put on a fluoroethylene resin-baked iron plate, and cured in an oven at 250° C. for 10 minutes. A rigid porous plate having a residual organic content of about 5% was obtained. The resulting rigid plate was further cured at 400° C. for 30 minutes.
  • a solution of 80 g of tetraethoxysilane (by Shin-etsu Chemical), 40 g of a solution of cyclohexyl acrylate (number-average molecular weight, 100,000) in ethyl acetate (solid content, 50%), and 2 g of dibutyltin dilaurate (by Wako Jun-yaku) was cast into a frame, width 10 mm ⁇ length 30 mm ⁇ depth 0.05 mm, formed of a polyethylene sheet with an adhesive tape, and cured at 20° C. for 48 hours while dried in air to evaporate ethyl acetate.
  • the resulting film was cured in an oven at 250° C. for 10 minutes.
  • a rigid porous plate was obtained, but it had a residual organic content of 30%.
  • the resulting rigid porous plate was further cured at 400° C. for 30 minutes, and its residual organic content reduced to at most 5%.
  • a precursor containing an alkoxysilane and a heat-decaying material is a liquid composite material where the alkoxysilane has partially hydrolyzed and condensed, and the composite material is used as an SOG (spin-on-glass) coating solution to form an interlayer insulating film between wirings of a semiconductor device.
  • SOG spin-on-glass
  • an element separation region 2 is selectively formed on a silicon substrate 1 according to a trench element separation process.
  • a gate insulating film 3 is formed;
  • a gate silicon layer 4 is formed of a polycrystalline silicon containing an effective impurity such as phosphorus; and impurity diffusion layers 5 a and 5 b to be a source/drain region are formed through ion implantation followed by subsequent heat treatment.
  • a spacer 3 s is formed of a silicon oxide film or the like, around the side wall of the gate silicon layer 4 .
  • a high-melting-point metal such as cobalt (Co) is deposited on the entire surface of the structure according to a sputtering process, then this is subjected to heat treatment to remove the unnecessary cobalt.
  • a high-melting-point metal such as cobalt (Co) is deposited on the entire surface of the structure according to a sputtering process, then this is subjected to heat treatment to remove the unnecessary cobalt.
  • silicide layers 6 g , 6 a and 6 b are selectively formed on the gate silicon layer 4 and the impurity diffusion layers 5 a and 5 b to make a silicide structure.
  • a first interlayer insulating film 7 is formed on the entire surface of the structure.
  • the first interlayer insulating film 7 is formed of a silicon oxide film through chemical vapor deposition (CVD) and its surface is planarized through chemical mechanical polishing (CMP).
  • CMP chemical mechanical polishing
  • a first contact hole 9 is formed in the first interlayer insulating film 7
  • a first wiring 8 is formed of a metal such as tungsten (W).
  • the thermal oxide film of silicon has a relative dielectric constant of 3.9, and the relative dielectric constant of the first interlayer insulating film 7 could be almost 4 or so though depending on the reaction gas used in CVD.
  • the above-mentioned SOG coating solution is applied onto the entire surface of the structure according to a spin-coating process at a rotation speed of from 1000 to 5000 rpm so that it covers the first interlayer insulating film 7 and the first wiring layer 8 .
  • the rotation speed is determined depending on the viscosity of the SOG coating solution or the thickness of the interlayer insulating film.
  • the film thus formed through the spin coating is subjected to first heat treatment in a diffusion furnace at 150° C. to 250° C. for 10 minutes or so. In that manner, a rigid and porous second interlayer insulating film 10 having a residual organic content of about 5% is formed, as in FIG. 1( e ).
  • the second interlayer insulating film 10 is subjected to second heat treatment in a diffusion furnace at 400° C. for 30 minutes.
  • the second interlayer insulating film 10 becomes a porous film having a thickness of, for example, 500 nm or so and having uniform-size pores uniformly dispersing in the film.
  • the relative dielectric constant of the second interlayer insulating film 10 could be from 1.5 to 2.5 or so.
  • the atmosphere gas for the first and second heat treatment may be oxygen or nitrogen.
  • the first heat treatment is effected in an oxygen gas atmosphere, then the coating film formed by the spin coating operation could be readily porous, and even at 130° C. or so, a uniform porous layer can be formed.
  • the temperature for forming the intended porous structure is higher than that in the oxygen gas atmosphere.
  • the solvent of the SOG coating solution is removed and the sol-like coating film formed by the spin coating operation is gelled.
  • a readily-gelling SOG coating solution is used, then it is desirable that the first heat treatment is effected in an oxygen gas atmosphere.
  • a hardly-gelling SOG coating solution is used, then it is desirable that the first heat treatment is effected in a nitrogen gas atmosphere.
  • a contact hole 11 is formed through the first interlayer insulating film 7 and the second interlayer insulating film 10 , and a second wiring layer 12 is formed of a metal such as aluminium (Al). Finally, a passivation film 13 is formed to cover the entire surface of the structure. In that manner, a two-layered wiring structure-having semiconductor device is formed, as in FIG. 1( e ). Though not shown herein, many other semiconductor elements are formed on the silicon substrate 1 .
  • an interlayer insulating film having pores of high uniformity and having a low dielectric constant can be formed stably in a semiconductor device.
  • the interlayer insulating film has good mechanical strength and good moisture absorption resistance.
  • a semiconductor device capable of being driven at high speed can be produced with high accuracy, and a high-reliability semiconductor device can be provided.
  • Example 23 the same porous material as that for the second interlayer insulating film 10 may be applied also to the first interlayer insulating film 7 .
  • the surface of the first interlayer insulating film 7 is made flat and it does not require CMP.
  • Example 23 it is easy like in Example 23 to use a porous material formed of the above-mentioned SOG coating solution as the low-dielectric-constant interlayer insulating film in a damascene structure or dual-damascene structure that uses copper as the wiring metal.
  • the interlayer insulating film is a low-dielectric-constant insulating film formed at low temperatures and capable of undergoing heat treatment at 400° C. or so, as so mentioned hereinabove.
  • the embodiments mentioned hereinabove are to demonstrate the formation of a porous material by the use of a siloxane skeleton-having polycondensation compound (hydrogen or organic-containing compound with an Si—O structure as the main backbone thereof), to which, however, the invention should not be limited.
  • the heat-decaying material of the invention is also applicable to production of porous materials of silicon-containing organic thin films having a main skeleton of an organic polymer.
  • the organic insulating film of the type applicable to the invention include, for example, BCB films (organic film formed of divinylsiloxane-benzocyclobutene polymer) and polyallyl ether-Si bond-having organic insulating films.
  • any other silicon-containing organic thin films having a main skeleton of organic polymer which generally comprise organosiloxane or aromatic and/or hydrocarbon chain-containing organosiloxane, are also usable herein.
  • the above-mentioned porous organic thin films may be formed in any film-forming method of a spin-on-coating method or a plasma polymerization method.
  • a spin-on-coating method When a spin-on-coating method is employed, then a main skeleton material monomer is first applied onto a substrate along with a heat-decaying material thereonto in a mode of spin-on-coating. Then, the coated substrate is annealed whereby the monomer is thermally polymerized on the substrate to form a silicon-containing organic thin film having an organic polymer as the main skeleton thereof.
  • a main skeleton material monomer and a monomer to give a heat-decaying material are vaporized to produce a monomer vapor. The monomer vapor is introduced into an inert gas and is further polymerized to form a silicon-containing organic thin film having an organic polymer as the main skeleton thereof.
  • insulating films of silsesquioxanes, or silica films containing at least one bond of Si—H bond, Si—CH 3 bond or Si—F bond may be formed.
  • the insulating films of silsesquioxanes include low-dielectric-constant films of methyl silsesquioxane, hydrogen silsesquioxane, methylated hydrogen silsesquioxane or fluorinated silsesquioxane.
  • the above-mentioned BCB film may have a silica content of about 20% and its relative dielectric constant before formed into a porous film may be 2.5 or so.
  • a composite film of the type that comprises such an organic component and a silica component or silicon component may also be the organic insulating film.
  • a composite film that comprises the organic component and the silica component or a partly nitrided silicon component may also be the organic insulating film.
  • the resulting resin sheet is an adhesive sheet having gel-like rubber elasticity.
  • conductive fine particles (trade name, Micropearl SOL, by Sekisui Chemical Industry) were sucked, and then adhered to and disposed on an adhesive sheet to produce a conductive particles transfer sheet.
  • the conductive particles transfer sheet was laid on a semiconductor chip packages having a large number of electrodes provided thereon, in such a manner that the position of the electrode of the semiconductor chip package could correspond to the position of the conductive fine particle and the conductive fine particle could be in direct contact with the electrode.
  • a liquid resin composition prepared by adding 3 parts by weight of a diacylphosphine oxide compound (trade name, Irgacure 819, by Ciba Specialty Chemical) to 100 parts by weight of a crosslinkable silyl group-having polyoxypropylene resin (trade name, MS Polymer S303, by Kanegafuchi Chemical Industry) was applied onto the surface of a polyethylene terephthalate (PET) film having a thickness of 25 ⁇ m to form thereon a coating layer that could have a dry thickness of 10 ⁇ m. This was exposed to UV rays and cured to obtain an adhesive sheet. The resulting sheet was sticky, and have gel-like rubber elasticity. Next, an electrolytic copper foil having a thickness of 12 ⁇ m was stuck to the adhesive sheet to produce a copper foil-stuck adhesive sheet.
  • a diacylphosphine oxide compound trade name, Irgacure 819, by Ciba Specialty Chemical
  • a dry film resist was stuck to the copper foil side of the copper foil-stuck adhesive sheet produced in the above, and this was exposed to light through a circuit-patterned photomask having a line width of 30 ⁇ m and a line-to-line distance of 30 ⁇ m, then developed and etched, and the resist was stripped away and washed to give a transfer sheet for circuit formation.
  • the copper foil circuit pattern side of the thus-obtained transfer sheet for circuit formation was positioned to a semi-cured, insulating substrate formed of glass epoxy, and hot-pressed in a nitrogen atmosphere at 130° C. to thereby bond the copper foil circuit pattern to the insulating substrate.
  • this was put into an oven at 180° C. in a nitrogen atmosphere, whereupon the heat-decaying resin decayed and the adhesive sheet peeled off, accordingly, the circuit pattern was accurately transferred onto the insulating substrate.
  • Example 31 In the same manner as in Example 31, a transfer sheet for circuit formation was fabricated which had a circuit pattern formed on the surface of an adhesive sheet but in which the line width of the circuit pattern was 20 ⁇ m.
  • the copper foil circuit pattern side of the thus-obtained transfer sheet for circuit formation was positioned to a semi-cured, insulating substrate formed of glass epoxy, and hot-pressed in a nitrogen atmosphere at 130° C. to thereby bond the copper foil circuit pattern to the insulating substrate.
  • this was put into an oven at 180° C. in a nitrogen atmosphere, and heated therein until the heat-decaying resin could decay and the adhesive sheet could peel off.
  • the hot-pressing was effected in a nitrogen atmosphere and when the structure was put into an oven, the decomposition gas was not generated all at a time and the circuit pattern having a line width of 20 ⁇ m was accurately transferred onto the insulating substrate since the oxygen concentration was kept low.
  • a transfer sheet for circuit formation was fabricated in the same manner as in Example 31.
  • the copper foil circuit pattern side of the thus-obtained transfer sheet for circuit formation was positioned to a ceramic green sheet, and hot-pressed at 130° C. whereby the copper foil circuit pattern was bonded to the ceramic green sheet.
  • this was put into an oven at 180° C. in a nitrogen atmosphere, whereupon the heat-decaying resin decayed and the adhesive sheet peeled off, accordingly, the circuit pattern was accurately transferred onto the ceramic green sheet.
  • an adhesive sheet 212 is formed in the same manner as in Example 31, and a metal layer 213 of copper for rearrangement wiring is formed on its surface to prepare a transfer sheet 211 for circuit formation.
  • the line width of the metal layer 213 is 10 ⁇ m or so, and the thickness thereof is 5 ⁇ m or so.
  • a semiconductor device which comprises a semiconductor chip 214 , an electrode pad 215 connected to the wiring layer inside the semiconductor chip 214 , and an insulating substrate 217 bonded to the semiconductor chip 214 via an adhesive layer 216 therebetween, and in which a through-hole is formed to run through the insulating substrate 217 and the adhesive layer 216 to reach the electrode pad 215 , and is filled with a conductive substance 218 , is bonded to the transfer sheet 211 for circuit formation in a mode of hot-pressing in a nitrogen atmosphere at 130° C.
  • the insulating substrate 217 is formed of a flexible material such as polyimide tape or a rigid material such as FR-4.
  • the adhesive layer 216 is formed of a thermosetting or thermoplastic adhesive.
  • the semiconductor device which comprises the semiconductor chip 214 , the electrode pad 215 connected to the wiring layer inside the semiconductor chip 214 , the insulating substrate 217 bonded to the semiconductor chip 214 via the adhesive layer 216 therebetween, the conductive substance 218 filled in the through-holes that runs through the insulating substrate 217 and the adhesive layer 216 to reach the electrode pad 215 , and which further comprises the metal layer 213 for rearrangement wiring that is electrically connected to the electrode pad 215 through the conductive substance 218 , and the solder bump 219 for connecting the device to an external packaging substrate.
  • the rearrangement wiring can be readily varied in accordance with the external packaging wiring substrate, and therefore the semiconductor device of the type has a broad latitude to satisfy various service conditions for various customers. Accordingly, the invention promotes fabrication of custom-made semiconductor devices in practicable packaging level.
  • the heating temperature is 200° C. or lower (solder bump-forming temperature) and is relatively low, and therefore, this does not change at all the properties of semiconductor chips. Accordingly, in the invention, electronic structures of CSP (chip-size package) semiconductor devices can be readily produced.
  • the heat-decaying material of the invention hardly deteriorates and decomposes at ordinary service temperatures, and when heated at relatively low temperatures, they may decay within a short period of time.
  • a precursor is prepared which contains a skeleton-forming crosslinkable material (a) and the heat-decaying material (b) of the invention that comprises a polyoxyalkylene resin as the principal ingredient thereof and decomposes and evaporates when heated, and the precursor is heated at a temperature not lower than the temperature at which the heat-decaying material decays under heat, whereby the heat-decaying material is decayed to form a large number of pores, and a porous material having as the matrix thereof, a crosslinked skeleton phase of the crosslinkable material (a) can be obtained. Accordingly, a porous material can be produced in a relatively simple process.
  • a precursor may be prepared by dispersing the heat-decaying material (b) in the skeleton-forming crosslinkable material (a), and when the heat-decaying material is merely uniformly dispersed therein, then a porous material having uniformly dispersed pores can be readily obtained.
  • the particle size of the dispersed particles of the heat-decaying material is controlled, then relatively large pores can be readily formed and a porous material having uniform-size pores can be readily produced.
  • the heat-decaying material completely decays when heated, it leaves little residue and does not almost increase the dielectric constant of the structure where the heat-decaying material has been decayed.
  • the heat-decaying material of the invention When the heat-decaying material of the invention is used, then conductive fine particles may be disposed accurately on the electrodes of electronic parts, not being shifted or dropped away. In addition, multiple electroconductive fine particles may be surely and readily connected to the electrodes of electronic parts all at a time. To that effect, the invention provides a conductive particles transfer sheet and a method for connecting conductive fine particles to electrodes, satisfying the requirements.
  • the electronic parts are meant to include semiconductor chips, resin-encapsulated semiconductor devices, packaging substrates such as printed boards on which these electronic parts are to be mounted.
  • conductive fine particles may be formed on a semiconductor wafer, and therefore semiconductor wafers are also within the scope of the electronic parts.
  • the conductive particles transfer sheet has conductive fine particles disposed in predetermined positions of a heat-decaying sheet. When heated, the sheet itself decays. Therefore, the transfer sheet is effective for bonding bumps or solder balls onto electronic parts such as semiconductor chips.
  • the adhesive sheet decays or its adhesive force lowers owing to the vapor generated through decomposition of the heat-decaying resin. Therefore, even when the adhesive sheet has a high adhesive force or even when it has a circuit pattern having an extremely narrow line width and when the circuit pattern is transferred from it, the circuit pattern can be well transferred onto an insulating substrate or a ceramic green sheet with no pattern disturbance. Accordingly, the invention makes it possible to produce circuit boards having further increased wiring density and enabling higher-density packaging, with high accuracy and at high producibility.
  • transfer sheet for circuit formation of the invention it is possible to transfer circuit patterns even onto substrates for liquid-crystal display panels, plasma display panels, etc.
  • pattern formation may be significantly simplified as compared with conventional photolithography. Accordingly, the invention makes it possible to further improve the accuracy in patterning technology for various materials and to further reduce the cost of patterning. As a result, the production costs of semiconductor devices can be thereby significantly reduced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Wire Bonding (AREA)
  • Non-Insulated Conductors (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)
US10/532,747 2002-11-29 2003-11-26 Heat-decaying materials, transfer sheet using the same, and patterning method Expired - Fee Related US7591921B2 (en)

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JP2002-0349195 2002-11-29
JP2002349195 2002-11-29
JP2002-349194 2002-11-29
JP2002349192 2002-11-29
JP2002-349192 2002-11-29
JP2002349194 2002-11-29
JP2003026330 2003-02-03
JP2003-026330 2003-02-03
JP2003049842 2003-02-26
JP2003-049842 2003-02-26
JP2003394620A JP2004256788A (ja) 2002-11-29 2003-11-25 加熱消滅性材料
JP2003-394620 2003-11-25
PCT/JP2003/015104 WO2004050762A1 (fr) 2002-11-29 2003-11-26 Matiere thermiquement evaporable, feuille de transfert utilisant une telle matiere, et procede de formation de motif

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CN100338139C (zh) 2007-09-19
CN1708555A (zh) 2005-12-14
EP1566410A1 (fr) 2005-08-24
JP2004207698A (ja) 2004-07-22
WO2004050762A1 (fr) 2004-06-17
EP1566410A4 (fr) 2011-06-22
KR20050083864A (ko) 2005-08-26
US20050276934A1 (en) 2005-12-15
JP2004256788A (ja) 2004-09-16
KR100806491B1 (ko) 2008-02-21
JP2004193594A (ja) 2004-07-08

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